Dyeing composition at acidic pH comprising a direct dye of triarylmethane structure

ABSTRACT

The present invention relates to a composition for dyeing keratin fibres comprising, in a cosmetically acceptable medium of acidic pH, the pH of which is preferably less than 5, one or more direct dyes of triarylmethane structure, which are preferably cationic. The invention also relates to a process for dyeing keratin fibres using said composition and also to a use for dyeing keratin fibres.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a national stage application of PCT/EP2016/081984, filedinternationally on Dec. 20, 2016, which claims priority to FrenchApplication No. 1562992 filed on Dec. 21, 2015, both of which areincorporated by reference herein in their entireties.

The present invention relates to a composition for dyeing keratinfibres, in particular human keratin fibres such as the hair, comprisingone or more direct dyes of triarylmethane structure, which arepreferably cationic, in an acidic medium, the pH of which is preferablyless than 5.

The invention also relates to a process for dyeing keratin fibres, andalso to the use thereof for dyeing keratin fibres.

Many people have sought for a long time to modify the colour of theirhair and in particular to mask their grey hair.

It is known practice to dye keratin fibres with dyeing compositionscontaining direct dyes. These compounds are coloured and colouringmolecules that have affinity for the fibres. It is known practice, forexample, to use direct dyes of the nitrobenzene type, anthraquinone ornitropyridine dyes, and dyes of the azo, xanthene, acridine, azine ortriarylmethane type.

These dyes are usually applied to fibres optionally in the presence ofan oxidizing agent if it is desired to obtain simultaneous lightening ofthe fibres. Once the leave-on time has elapsed, the fibres are rinsed,optionally washed and dried.

The colourings resulting from the use of direct dyes are colourings thatare often chromatic but are, however, only temporary or semi-permanentsince the nature of the interactions that bind the direct dyes to thekeratin fibre and their desorption from the surface and/or the core ofthe fibre are responsible for their weak dyeing power and their poorrelative persistence with respect to washing or perspiration. Thus, thecolourings may also not be sufficiently fast in the face of externalagents such as light, shampoos and perspiration.

It is known practice to use compounds of triarylmethane type to obtain avery chromatic keratin fibre colouring. However, it has been observedthat their dyeing power is limited and sometimes insufficient forproviding good intensity. Furthermore, it has been observed that thecolourings obtained exhibit poor fastness with respect to washing, inparticular on sensitized hair, in particular bleached hair.

The aim of the present invention is to provide a dyeing compositionwhich results in good dyeing properties.

In particular, one of the aims of the present invention is to providedirect dyeing compositions that make it possible to obtain a strong,chromatic, aesthetic, sparingly selective colouring with varied shades,which shows good resistance to the various attacking factors to whichthe hair may be subjected, such as shampoos and/or light, sweat andpermanent reshaping, and which can be faded out easily.

One particular objective of the invention is to provide compositions fordyeing hair that has previously been lightened.

This aim is achieved by means of the present invention, a subject ofwhich is in particular a composition for dyeing keratin fibres such asthe hair, comprising, in a cosmetically acceptable medium of acid pH,preferably less than 5, one or more direct dyes of triarylmethanestructure, which are preferably cationic.

The applicant has thus discovered that formulating these direct dyes oftriarylmethane structure in this specific support makes it possible toobtain a very good development of the colour, very strong colours, with,where appropriate, a decrease in selectivity and better fastness, inparticular better fastness with respect to washing.

Moreover, the dyeing compositions according to the present inventionmake it possible to achieve a wide range of colours with varied shades.

In particular, the compositions in accordance with the invention make itpossible to lead to satisfactory colour build-up, especially ondepigmented keratin fibres, such as grey hair.

For the purposes of the present invention, the term “build-up” of thecolour of keratin fibres is intended to mean the variation in colouringbetween locks of undyed grey hair and locks of dyed hair.

Other subjects, characteristics, aspects and advantages of the presentinvention will emerge even more clearly on reading the description andthe examples that follow.

In that which follows and unless otherwise indicated, the limits of arange of values are included in this range.

The expression “at least one” is equivalent to the expression “one ormore”.

Direct Dyes of Triarylmethane Structure:

The composition according to the invention comprises one or more directdye(s) of triarylmethane structure.

Preferably, the total content of direct dye(s) of triarylmethanestructure ranges from 0.0001% to 10% by weight, preferably from 0.0005%to 5% by weight and better still from 0.00075% to 3% by weight relativeto the total weight of the composition.

In particular, the triarylmethane dye(s) of the invention may beanionic, cationic, neutral or zwitterionic.

Preferably, the dye(s) of the invention are chosen from thetriarylmethane dyes of formula (I):

and also the organic or mineral, acid or base addition salts thereof,the geometrical isomers, optical isomers and tautomers thereof, and themesomeric forms thereof, and the solvates such as hydrates;

in which formula (I), A, B and C are identical or different, andrepresent a (hetero)aryl group such as phenyl which is optionallysubstituted,

represents a single bond or a double bond.

The direct dyes of formula (I) can thus be cationic, anionic, non-ionicor zwitterionic.

According to one particularly preferred embodiment of the invention, thetriarylmethane dye(s) are cationic.

The term “cationic direct dye” is commonly intended to mean dyesreferred to as “basic direct dyes” or “basic dyes” owing to theiraffinity with acidic substances.

The term “cationic direct dyes” is intended to mean any direct dyecomprising in particular in its structure at least one endocyclic orexocyclic, cationic or cationizable group. In particular, the charge maybe borne by an aryl or heteroaryl group.

Preferably, the triarylmethane direct dye(s) according to the inventionare cationic dyes of formulae (IIa) and (II′a) below:

and also the organic or mineral, acid or base addition salts thereof,the geometrical isomers, optical isomers and tautomers thereof, and themesomeric forms thereof, and the solvates thereof such as hydrates:

in which formulae (IIa) and (II′a) below:

-   -   R1, R2, R3 and R4, which may be identical or different,        represent a hydrogen atom or a (C₁-C₆)alkyl group which is        optionally substituted, preferably with a hydroxyl group, an        aryl group such as phenyl, an aryl(C₁-C₄)alkyl group such as        benzyl, a heteroaryl, or a heteroaryl(C₁-C₄)alkyl group, or else        two groups R1 and R2, and/or R3 and R4, borne by the same        nitrogen atom, form, together with the nitrogen atom which bears        them, an optionally substituted heterocycloalkyl group such as        morpholino, piperazino or piperidino; preferably, R1, R2, R3 and        R4, which may be identical or different, represent a hydrogen        atom or a (C₁-C₄)alkyl group;    -   R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16, which        may be identical or different, represent a hydrogen atom, a        halogen atom, or a group chosen from i) hydroxyl; ii)        thiol; iii) amino; iv) (di)(C₁-C₄)(alkyl)amino; v) (di)arylamino        such as (di)phenylamino; vi) nitro; vii) acylamino (—NR—C(O)R′)        in which the radical R is a hydrogen atom or a C₁-C₄ alkyl        radical optionally bearing at least one hydroxyl group, and the        radical R′ is a C₁-C₂ alkyl radical; viii) carbamoyl        ((R)2N—C(O)—) in which the radicals R, which may be identical or        different, represent a hydrogen atom or a C₁-C₄ alkyl radical        optionally bearing at least one hydroxyl group; ix) carboxylic        acid or ester, (—O—C(O)R′) or (—C(O)OR′), in which the radical        R′ is a hydrogen atom, or C₁-C₄ alkyl optionally bearing at        least one hydroxyl group and the radical R′ is a C₁-C₂ alkyl        radical; x) alkyl optionally substituted in particular with a        hydroxyl group; xi) alkylsulfonylamino (R′SO₂—NR—) in which the        radical R represents a hydrogen atom or a C₁-C₄ alkyl radical        optionally bearing at least one hydroxyl group and the radical        R′ represents a C₁-C₄ alkyl radical or a phenyl radical; xii)        aminosulfonyl ((R)2N—SO₂—) in which the radicals R, which may be        identical or different, represent a hydrogen atom or a C₁-C₄        alkyl radical optionally bearing at least one hydroxyl        group; xiii) (C₁-C₄)alkoxy; and xiv) (C₁-C₄)alkylthio;    -   or else two radicals borne by two contiguous carbon atoms R5 and        R6 and/or R7 and R8 and/or R9 and R10 and/or R11 and R12 and/or        R13 and R14 and/or R15 and R16 form, together with the carbon        atoms which bear them, an aryl or heteroaryl, preferably benzo,        6-membered fused ring cycle, said ring possibly also being        optionally substituted, preferably an unsubstituted benzo ring;    -   Q- represents an anionic counterion for achieving        electroneutrality, preferably chosen from halides such as        chloride or bromide, and phosphate.

When the cationic dye comprises one or more anionic substituents such asCOOR or SO₃R with R denoting a hydrogen or a cation, it is understoodthat there are then more cationic substituents than anionicsubstituents, such that the overall resulting charge of thetriarylmethane structure is cationic.

According to one preferred embodiment, the triarylmethane dye(s) of theinvention is (are) chosen from those of formula (IIa) or (II′a), inwhich, taken together or separately,

-   -   R1, R2, R3 and R4 represent a hydrogen atom or a (C₁-C₄)alkyl        group such as methyl or ethyl,    -   R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16        represent a hydrogen atom, a halogen atom, such as chlorine, or        a (C₁-C₄)alkyl group such as methyl or ethyl, an amino group, or        a (di)(C₁-C₄)(alkyl)amino group, and preferably at least one of        the groups R9, R10, R11 or R12 represents a hydrogen atom, a        halogen atom (C₁), or an amino group, or a (C₁-C₄)(alkyl)amino        or (di)(C₁-C₄)(alkyl)amino group, preferably in the position        para to the phenyl group.

Preferably, the direct dye(s) of triarylmethane structure are chosenfrom Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4,Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic Green1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

The term “anionic counterion” is intended to mean an anion or an anionicgroup derived from an organic or mineral acid salt which counterbalancesthe cationic charge of the dye; more particularly, the anioniccounterion is chosen from: i) halides such as chloride or bromide; ii)nitrates; iii) sulfonates, including C₁-C₆ alkylsulfonates: Alk-S(O)₂O⁻such as methanesulfonate or mesylate and ethanesulfonate; iv)arylsulfonates: Ar—S(O)₂O⁻ such as benzenesulfonate and toluenesulfonateor tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate;ix) alkyl sulfates: Alk-O—S(O)O⁻ such as methyl sulfate and ethylsulfate; x) aryl sulfates: Ar—O—S(O)O⁻ such as benzene sulfate andtoluene sulfate; xi) alkoxy sulfates: Alk-O—S(O)₂O⁻ such as methoxysulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar—O—S(O)₂O⁻, xiii)phosphates O═P(OH)₂—O⁻, O═P(O⁻)₂—OH, O═P(O⁻)₃,HO—[P(O)(O⁻)]_(w)—P(O)(O⁻)₂ with w being an integer; xiv) acetate; xv)triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate(O=)₂S(O⁻)₂ or SO₄ ²⁻ and monosulfate HSO₄ ⁻.

The anionic counterion, derived from an organic or mineral acid salt,ensures the electroneutrality of the molecule. Thus, it is understoodthat, when the anion comprises several anionic charges, then the sameanion can be used for the electroneutrality of several cationic groupsin the same molecule or else can be used for the electroneutrality ofseveral molecules. For example, a disulfide dye of formula (I) whichcontains two cationic chromophores can either contain two “singlycharged” anionic counterions or contains a “doubly charged” anioniccounterion, such as (O=)₂S(O⁻)₂ or O═P(O⁻)₂—OH.

The term “cationic counterion” is intended to mean alkali metal cations,alkaline-earth metal cations or organic cations such as ammoniums,preferably the anionic counterions of the invention are chosen fromalkali metals such as N⁺ or K⁺.

A “cationic heteroaryl radical” is a heteroaryl group as defined abovewhich comprises an endocyclic or exocyclic quaternized cationic group.

When the cationic charge is endocyclic, it is included in the electrondelocalization via the mesomeric effect, for example it is a pyridinium,imidazolium or indolinium group:

with R and R′ being a heteroaryl substituent as defined above andparticularly a (hydroxy)(C₁-C₈)alkyl group such as methyl.

When the charge is exocyclic, for example, it involves an ammonium orphosphonium substituent R⁺ such as trimethylammonium, which is outsidethe heteroaryl such as pyridyl, indolyl, imidazolyl or naphthalimidyl inquestion;

with R a heteroaryl substituent as defined above and R⁺ an ammoniumRaRbRcN⁺—, phosphonium RaRbRcP⁺- or ammonium RaRbRcN⁺—(C₁-C₆)alkylaminogroup with Ra, Rb and Rc, which are identical or different, representinga hydrogen atom or a (C₁-C₈)alkyl group, such as methyl.

A “cationic aryl carrying an exocyclic charge” is intended to mean anaryl ring of which the quaternized cationic group is outside said ring;it is especially an ammonium or phosphonium R⁺ substituent, such astrimethylammonium, which is outside the aryl, such as phenyl ornaphthyl:

Preferably, the total content of cationic direct dye(s) oftriarylmethane structure is between 0.0001% and 10% by weight,preferably between 0.0005% and 5% by weight and better still 0.00075%and 3% by weight relative to the total weight of the composition.

According to another embodiment, the dye(s) of triarylmethane structureis (are) chosen from anionic dyes of triarylmethane structure.

The term “anionic direct dyes” is intended to mean any direct dyecomprising in its structure at least one sulfonate SO₃— group and/or atleast one carboxylate group C(O)O— and optionally one or more anionicgroups G- with G-, which may be identical or different, representing ananionic group chosen from alkoxide O—, thiolate S—, carboxylate andthiocarboxylate: C(Q)Q′-, with Q and Q′, which may be identical ordifferent, representing an oxygen or sulfur atom; preferably, G-represents a carboxylate, i.e. Q and Q′ represents an oxygen atom.

In particular, the term “anionic direct dyes” is commonly intended tomean dyes referred to as “acid direct dyes” owing to their affinity withalkaline substances. The term “anionic direct dyes” is intended to meanany direct dye comprising in its structure at least one CO₂R or SO₃Rsubstituent with R denoting a hydrogen atom or a cation originating froma metal or from an amine, or an ammonium ion.

When the anionic dye comprises one or more cationic substituents, it isunderstood that there are then more anionic substituents than cationicsubstituents, such that the overall resulting charge of thetriarylmethane structure is anionic. A group is said to be “bearing aquaternizable cationic group” when it comprises at least one tertiaryamine or tertiary phosphine at the end of a hydrocarbon-based chain,preferably C₁-C₁₀ alkyl, such as —(CR′R″)p-N(Ra)—Rb with R′ and R″,which may be identical or different, representing a hydrogen atom or a(C₁-C₆) alkyl group; Ra and Rb, which may be identical or different,representing a (poly)(hydroxy)(C₁-C₆)alkyl group or Ra and Rb form,together with the nitrogen atom that bears them, a heterocycloalkylgroup such as morpholino, piperidino or piperazino; and p representingan integer between 1 and 10 inclusive; preferably, R′ and R″ represent ahydrogen atom, Ra and Rb represent a (C₁-C₄)alkyl group and p is between2 and 5.

The “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of aradical may be substituted with at least one substituent borne by acarbon atom, chosen from:

-   -   a C₁-C₁₆, preferably C₁-C₈, alkyl radical optionally substituted        with one or more radicals chosen from the radicals hydroxyl,        C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, acylamino or amino        substituted with two identical or different C₁-C₄ alkyl radicals        which optionally bear at least one hydroxyl group or it being        possible for the two radicals to form, with the nitrogen atom to        which they are attached, a saturated or unsaturated and        optionally substituted 5- to 7-membered and preferably 5- or        6-membered heterocycle optionally comprising another nitrogen or        non-nitrogen heteroatom;    -   a halogen atom such as chlorine, fluorine or bromine;    -   a hydroxyl group;    -   a C₁-C₂ alkoxy radical;    -   a (poly)hydroxy(C₂-C₄)alkoxy radical;    -   an amino radical;    -   nitro;    -   a 5- or 6-membered heterocycloalkyl radical;    -   an optionally cationic 5- or 6-membered heteroaryl radical,        preferentially imidazolium, optionally substituted with a        (C₁-C₄)alkyl radical, preferentially methyl;    -   an amino radical substituted with one or two identical or        different C₁-C₆ alkyl radicals, optionally bearing at least:    -   a hydroxyl group,    -   an amino group optionally substituted with one or two optionally        substituted C₁-C₃ alkyl radicals, said alkyl radicals possibly        forming with the nitrogen atom to which they are attached a        saturated or unsaturated, optionally substituted 5- to        7-membered heterocycle, optionally comprising at least one other        nitrogen or non-nitrogen heteroatom,    -   an acylamino (—NR—C(O)R′) radical in which the R radical is a        hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at        least one hydroxyl group and the R′ radical is a C₁-C₂ alkyl        radical;    -   a carbamoyl ((R)2N—C(O)—) radical in which the R radicals, which        may be identical or different, represent a hydrogen atom or a        C₁-C₄ alkyl radical optionally bearing at least one hydroxyl        group;    -   a carboxylic acid or ester radical, (—O—C(O)R′) or (—C(O)OR′),        in which the radical R′ is a hydrogen atom or a C₁-C₄ alkyl        radical optionally bearing at least one hydroxyl group, and the        radical R′ is a C₁-C₂ alkyl radical;    -   the carboxylic radical possibly being in acid or salified form        (preferably with an alkali metal or a substituted or        unsubstituted ammonium);    -   an alkylsulfonylamino radical (R'SO₂—NR—) in which the radical R        represents a hydrogen atom or a C₁-C₄ alkyl radical optionally        bearing at least one hydroxyl group and the radical R′        represents a C₁-C₄ alkyl radical, or a phenyl radical;    -   an aminosulfonyl radical ((R)2N—SO₂—) radical in which the R        radicals, which may be identical or different, represent a        hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at        least one hydroxyl group;    -   (O)₂S(O⁻)—, M+ with M+ representing a hydrogen atom or a        cationic counterion;    -   (O)CO⁻—, M⁺ with M⁺ as defined previously;    -   a cyano group (CN);    -   a (poly)haloalkyl group, preferably trifluoromethyl (CF₃).

The cyclic or heterocyclic part of a non-aromatic radical may besubstituted with at least one substituent borne by a carbon atom, chosenfrom the groups:

-   -   hydroxyl,    -   C₁-C₄ alkoxy or C₂-C₄ (poly)hydroxyalkoxy;    -   alkylcarbonylamino ((RC(O)—NR′—) in which the radical R′ is a        hydrogen atom, or a C₁-C₄ alkyl radical optionally bearing at        least one hydroxyl group and the radical R is a C₁-C₂ alkyl        radical or an amino radical substituted with two identical or        different C₁-C₄ alkyl groups optionally bearing at least one        hydroxyl group, said alkyl radicals possibly forming, with the        nitrogen atom to which they are attached, a saturated or        unsaturated, optionally substituted 5- to 7-membered heterocycle        optionally comprising at least one other nitrogen or        non-nitrogen heteroatom;    -   alkylcarbonyloxy ((RC(O)—O—) in which the radical R is a C₁-C₄        alkyl radical or an amino radical substituted with two identical        or different C₁-C₄ alkyl groups optionally bearing at least one        hydroxyl group, said alkyl radicals possibly forming, with the        nitrogen atom to which they are attached, a saturated or        unsaturated, optionally substituted 5- to 7-membered        heterocycle, optionally comprising at least one other nitrogen        or non-nitrogen heteroatom;    -   alkoxycarbonyl ((RO—C(O)—) in which the radical R is a C₁-C₄        alkyl radical or an amino radical substituted with two identical        or different C₁-C₄ alkyl groups optionally bearing at least one        hydroxyl group, said alkyl radicals possibly forming, with the        nitrogen atom to which they are attached, a saturated or        unsaturated, optionally substituted 5- to 7-membered        heterocycle, optionally comprising at least one other nitrogen        or non-nitrogen heteroatom.

A cyclic or heterocyclic radical or a non-aromatic part of an aryl orheteroaryl radical may also be substituted with one or more oxo groups.

An “aryl” radical represents a monocyclic or fused or non-fusedpolycyclic group comprising from 6 to 22 carbon atoms, at least one ringof which is aromatic; the aryl radical is in particular a phenyl,biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl and morepreferably phenyl.

A “heteroaryl” radical represents a 5- to 22-membered, monocyclic orfused or non-fused polycyclic group, comprising from 1 to 6 heteroatomschosen from nitrogen, oxygen, sulfur and selenium atoms, at least onering of which is aromatic; preferentially, a heteroaryl radical ischosen from acridinyl, benzimidazolyl, benzobistriazolyl,benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl,benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl,imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl,naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl,phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl,pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl,tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl,thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthyl and the ammoniumsalt thereof.

A “cyclic” radical is a “cycloalkyl” radical, i.e. a non-aromaticmonocyclic or fused or non-fused polycyclic radical containing from 5 to22 carbon atoms, which may comprise one or more unsaturations, such ascyclohexyl or cyclopentyl.

A “heterocyclic” radical is a non-aromatic, monocyclic or polycyclic,fused or non-fused 5- to 22-membered radical, comprising from 1 to 6heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms,morpholinyl, thiomorpholinyl, piperidyl, piperazinyl, pyrrolidinyl,tetrahydrofuranyl, tetrahydrothiophenyl, azepanyl, thioazepanyl;preferentially pyrrolidinyl and morpholino.

An “alkyl” radical is a linear or branched C₁-C₁₆, preferably C₁-C₈ andparticularly C₁-C₄ hydrocarbon-based radical, such as methyl or ethyl.

An “alkenyl” radical is a linear or branched C₂-C₂₀ hydrocarbon-basedradical comprising one or more conjugated or unconjugated double bonds,in particular a linear or branched C₄-C₁₀ radical comprising one, two orthree double bonds, preferentially only one double bond.

The term “optionally substituted” attributed to the alkyl radicalimplies that said alkyl radical may be substituted with one or moreradicals chosen from the following radicals: i) hydroxyl, ii) C₁-C₄alkoxy, iii) acylamino, iv) amino optionally substituted with one or twoidentical or different C₁-C₄ alkyl radicals, said alkyl radicalspossibly forming, with the nitrogen atom that bears them, a 5- to7-membered heterocycle, optionally comprising another nitrogen ornon-nitrogen heteroatom.

An “alkoxy” radical is an alkyl-oxy or alkyl-O— radical for which thealkyl radical is a linear or branched C₁-C₁₆, preferentially C₁-C₈,particularly C₁-C₄ hydrocarbon-based radical such as methoxy or ethoxy,and when the alkoxy group is optionally substituted, this implies thatthe alkyl group is optionally substituted as defined above.

A “(poly)haloalkyl” radical is an “alkyl” radical as defined above, inwhich one or more hydrogen atoms are substituted or replaced with one ormore halogen atoms such as the fluorine, chlorine or bromine atom; apolyhaloalkyl that may be mentioned is the trifluoromethyl group.

An “alkylthio” radical is an alkyl-S— radical for which the alkylradical is a linear or branched C₁-C₁₆, preferentially C₁-C₈,particularly C₁-C₄ hydrocarbon-based radical such as methylthio orethylthio, and when the alkylthio group is optionally substituted, thisimplies that the alkyl group is optionally substituted as defined above.

A cationic counterion is organic or mineral and preferentially chosenfrom alkali metal or alkaline-earth metal cations such as Na, Mg, K andCa, and organic cations such as ammonium NH₄ ⁺.

In particular, the anionic direct dye(s) are chosen from thetriarylmethane dyes of formulae (IIb) and (II′b):

in which formulae (IIb) and (II′b):

R33, R34, R35 and R36, which may be identical or different, represent ahydrogen atom or a group chosen from alkyl, optionally substituted aryland optionally substituted arylalkyl; particularly an alkyl group andbenzyl optionally substituted with a group (O)mS(O⁻)—, M+ with M+ and mas defined previously;

R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical ordifferent, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

amino, (di)(alkyl)amino;

hydroxyl, mercapto;

nitro, nitroso;

R^(∘)—C(X)—X′—, R^(∘)—X′—C(X)—, R^(∘)—X′—C(X)—X″— with R^(∘)representing a hydrogen atom or an alkyl or aryl group; X, X′ and X″,which may be identical or different, representing an oxygen or sulfuratom, or NR with R representing a hydrogen atom or an alkyl group;

—(O)₂S(O⁻)—, M⁺ with M⁺ representing a hydrogen atom or a cationiccounterion;

(O)C₀ ⁻—, M⁺ with M⁺ as defined previously;

or alternatively two contiguous groups R41 with R42 or R42 with R43 orR43 with R44 together form a fused benzo group: I′; with I′ optionallysubstituted with one or more groups chosen from i) nitro; ii) nitroso;iii) (O)2S(O⁻)—, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino;vii) R^(∘)—C(X)—X′—; viii) R^(∘)—X′—C(X)—; ix) R^(∘)—X′—C(X)—X″—; withM+, R^(∘), X, X′, X″ as defined previously.

Particularly, R37 to R40 represent a hydrogen atom, and R41 to R44,which may be identical or different, represent a hydroxyl group or(O)2S(O⁻)—, M⁺; and when R43 with R44 together form a benzo group, it ispreferentially substituted with a group (O)2S(O⁻)—;

it being understood that at least one of the rings G, H, I or I′comprises at least one sulfonate radical (O)2S(O⁻)— or a carboxylateradical —C(O)O—; preferentially sulfonate.

As examples of dyes of formulae (IIb) and (II′b), mention may be madeof: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49,Acid Green 3, Acid Green 5 and Acid Green 50.

According to one particular embodiment, the triarylmethane dye(s) of theinvention are fluorescent.

The term “fluorescent dye” is intended to mean a dye as definedpreviously, which, besides being coloured, is fluorescent, i.e. it hasthe capacity of re-emitting at least part of the light absorbed in thevisible range at a wavelength longer than that absorbed. In particular,the fluorescent dye is capable of absorbing in the UV or visibleradiation range at a wavelength λabs of between 250 and 800 nm andcapable of re-emitting in the visible range at an emission wavelengthλem of between 400 and 800 nm. Preferably, the fluorescent dye is a dyein the orange-colour range.

According to the present invention, the term “dye” is intended to mean acompound which has the capacity of colouring and which is in the form ofa coloured compound that may be observed with the naked eye, i.e.absorbing light at a wavelength between the UV and visible radiationrange, at a wavelength λabs of between 250 and 800 nm, particularly inthe visible spectrum between 400 and 700 nm.

Preferably, the dyes of the invention are dyes which absorb in theviolet and/or blue range, i.e. at an absorption wavelength which isincluded in the blue-violet range, particularly between 550 and 700 nm,more particularly between 580 and 680 nm.

According to one particular embodiment, when the triarylmethane dye(s)is (are) chosen from dyes which absorb in the blue and/or violet range,the composition may also comprise at least one additional direct dye(which may or may not be a triarylmethane), preferably which absorbs inthe orange or red range, preferably in the red range, such as, forexample, Acid Red 92.

Preferably, the dyes of triarylmethane structure are chosen from BasicViolet 2, Basic Blue 1 and/or Basic Blue 77 (also known as HC Blue 15),and mixtures thereof, better still from Basic Violet 2 and/or Basic Blue77 (also known as HC Blue 15), and mixtures thereof

Medium

The cosmetically acceptable medium that is suitable for dyeing, alsoknown as the dye support, generally comprises water or a mixture ofwater and of at least one organic solvent to dissolve the compounds thatare not sufficiently water-soluble.

More particularly, the organic solvents are chosen from linear orbranched and preferably saturated monoalcohols or diols, containing 2 to10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexyleneglycol (2-methyl-2,4-pentanediol), neopentyl glycol and3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol andphenylethyl alcohol; glycols or glycol ethers, for instance ethyleneglycol monomethyl, monoethyl and monobutyl ethers, propylene glycol orethers thereof, for instance propylene glycol, butylene glycol ordipropylene glycol monomethyl ether; and also diethylene glycol alkylethers, especially of C₁-C₄, for instance diethylene glycol monoethylether or monobutyl ether, alone or as a mixture.

The common solvents described above, if they are present, usuallyrepresent from 1% to 40% by weight and more preferentially from 5% to30% by weight relative to the total weight of the composition.

pH of the Medium

The pH of the dyeing composition according to the invention is acidic.For the purposes of the present invention, the term “acidic” is intendedto mean less than 7.

Preferably, the pH of the composition according to the invention is lessthan 5, and particularly ranges from 1 to 4.9.

Particularly preferably, the pH of the composition is between 2 and 4.5.

pH Adjuster

The cosmetically acceptable medium can be adjusted to the desired valueby means of acidifying or basifying agents usually used in the dyeing ofkeratin fibres, or alternatively using standard buffer systems.

Among the acidifying agents, examples that may be mentioned includemineral acids, for instance hydrochloric acid, nitric acid or sulfuricacid, or organic acids, for instance compounds comprising at least onecarboxylic acid function such as acetic acid, tartaric acid, citric acidor lactic acid, a sulfonic acid function, a phosphonic acid function ora phosphoric acid function.

Preferably, citric acid is used as acidifying agent.

The basifying agent(s) may be mineral, organic or hybrid.

The mineral alkaline agent(s) are preferably chosen from aqueousammonia, alkali metal carbonates or bicarbonates such as sodium orpotassium carbonates and sodium or potassium bicarbonates, sodiumhydroxide or potassium hydroxide, or mixtures thereof.

The organic alkaline agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6. It should be noted that it is thepK_(b) corresponding to the function of highest basicity. In addition,the organic amines do not comprise any alkyl or alkenyl fatty chaincomprising more than ten carbon atoms.

The organic alkaline agent(s) are chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds having formula (XII) below:

in which W is a divalent C₁ to C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁ to C₆ alkylradical, and/or optionally interrupted with one or more heteroatoms suchas O, or NR_(u); R_(x), R_(y), R_(z), R_(t) and R_(u), which may beidentical or different, represent a hydrogen atom or a C₁ to C₆ alkyl,C₁ to C₆ hydroxyalkyl or C₁ to C₆ aminoalkyl radical.

Examples of amines of formula (IX) that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” is intended to mean an organic amine comprisinga primary, secondary or tertiary amine function, and one or more linearor branched C₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

Organic amines chosen from alkanolamines such as monoalkanolamines,dialkanolamines or trialkanolamines comprising one to three identical ordifferent C₁-C₄ hydroxyalkyl radicals are in particular suitable forperforming the invention.

Among the compounds of this type, mention may be made ofmonoethanolamine (MEA), diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethyl)aminomethane.

More particularly, the amino acids that may be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function chosen more particularly from carboxylic acid,sulfonic acid, phosphonic acid and phosphoric acid functions. The aminoacids may be in neutral or ionic form.

As amino acids that may be used in the composition according to thepresent invention, mention may be made in particular of aspartic acid,glutamic acid, alanine, arginine, ornithine, citrulline, asparagine,carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine,leucine, methionine, N-phenylalanine, proline, serine, taurine,threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising anadditional amine function optionally included in a ring or in a ureidofunction.

Such basic amino acids are preferably chosen from those corresponding toformula (XIII) below, and also salts thereof:R—CH₂—CH(NH₂)—C(O)—OH  (XIII)

in which R represents a group chosen from imidazolyl, preferablyimidazolyl-4-yl; aminopropyl; aminoethyl;—(CH₂)₂N(H)—C(O)—NH₂; and —(CH₂)₂—N(H)—C(NH)—NH₂.

The compounds corresponding to formula (XIII) are histidine, lysine,arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may in particular be made of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. Asamino acid dipeptides that may be used in the present invention, mentionmay be made especially of carnosine, anserine and balenine.

The organic amine may also be chosen from compounds comprising aguanidine function. As amines of this type that may be used in thepresent invention, besides arginine, which has already been mentioned asan amino acid, mention may be made in particular of creatine,creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine,metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Hybrid compounds that may be mentioned include the salts of the aminesmentioned previously with acids such as carbonic acid or hydrochloricacid.

Guanidine carbonate or monoethanolamine hydrochloride may be used inparticular.

Preferably, the alkaline agent(s) present in the composition accordingto the invention are chosen from aqueous ammonia, alkanolamines, aminoacids in neutral or ionic form, in particular basic amino acids, andpreferably corresponding to those having formula (XIII).

The mineral basifying agent(s) are preferably chosen from mineralalkaline agents, preferably chosen from aqueous ammonia, alkali metalcarbonates or bicarbonates such as sodium or potassium carbonates andsodium or potassium bicarbonates, sodium hydroxide or potassiumhydroxide or mixtures thereof, better still from sodium hydroxide orpotassium hydroxide or mixtures thereof.

Additives

The composition according to the invention preferably comprises one ormore additives that may in particular be chosen from amino silicones,surfactants, thickening polymers, cationic polymers, fatty substancesand/or direct dyes other than dyes of triarylmethane structure, andmixtures thereof.

Aminated Silicone

The composition according to the invention may comprise one or moreamino silicones. The term “amino silicone” denotes any siliconecomprising at least one primary, secondary or tertiary amine or aquaternary ammonium group.

The weight-average molecular masses of these amino silicones may bemeasured by gel permeation chromatography (GPC) at ambient temperature(25° C.), as polystyrene equivalents. The columns used are μ styragelcolumns. The eluent is THF and the flow rate is 1 ml/min. 200 μl of a0.5% by weight solution of silicone in THF are injected. Detection isperformed by refractometry and UV-metry.

Preferably, the amino silicone(s) that may be used in the context of theinvention are chosen from:

a) the polysiloxanes corresponding to formula (A):

in which x′ and y′ are integers such that the weight-average molecularweight (Mw) is between 5000 and 500 000 approximately;

b) the amino silicones corresponding to formula (B):R′aG3-a-Si(OSiG2)n-(OSiGbR′2-b)m-O—SiG3-a-R′a  (B)

in which:

-   -   G, which may be identical or different, denotes a hydrogen atom        or a phenyl, OH or C₁-C₈ alkyl group, for example methyl, or a        C₁-C₈ alkoxy, for example methoxy,    -   a, which may be identical or different, denotes 0 or an integer        from 1 to 3, in particular 0,    -   b denotes 0 or 1, in particular 1,    -   m and n are numbers such that the sum (n+m) ranges from 1 to        2000, in particular from 50 to 150, it being possible for n to        denote a number from 0 to 1999 and especially from 49 to 149,        and for m to denote a number from 1 to 2000 and especially from        1 to 10;    -   R′, which may be identical or different, denotes a monovalent        radical of formula —CqH2qL in which q is a number ranging from 2        to 8 and L is an optionally quaternized amino group chosen from        the following groups:        —N(R″)2; —N+(R″)3 A-; —NR″-Q-N(R″)2 and —NR″-Q-N+(R″)3 A-,

in which R″, which may be identical or different, denotes hydrogen,phenyl, benzyl, or a saturated monovalent hydrocarbon-based radical, forexample a C₁-C₂₀ alkyl radical; Q denotes a linear or branched CrH2rgroup, r being an integer ranging from 2 to 6, preferably from 2 to 4;and A- represents a cosmetically acceptable anion, especially a halidesuch as fluoride, chloride, bromide or iodide.

Preferably, the amino silicones are chosen from the amino silicones offormula (B). Preferably, the amino silicones of formula (B) are chosenfrom amino silicones corresponding to formulae (C), (D), (E), (F) and/or(G) below.

According to a first embodiment, the amino silicones corresponding toformula (B) are chosen from silicones known as “trimethylsilylamodimethicone”, corresponding to formula (C):

in which m and n are numbers such that the sum (n+m) ranges from 1 to2000 and in particular from 50 to 150, it being possible for n to denotea number from 0 to 1999 and especially from 49 to 149, and for m todenote a number from 1 to 2000 and especially from 1 to 10.

According to a second embodiment, the amino silicones corresponding toformula (B) are chosen from the silicones of formula (D) below:

in which:

-   -   m and n are numbers such that the sum (n+m) ranges from 1 to        1000 and in particular from 50 to 250 and more particularly from        100 to 200; it being possible for n to denote a number from 0 to        999 and in particular from 49 to 249 and more particularly from        125 to 175, and for m to denote a number from 1 to 1000 and in        particular from 1 to 10, and more particularly from 1 to 5;    -   R1, R2 and R3, which may be identical or different, represent a        hydroxyl or C₁-C₄ alkoxy radical, at least one of the radicals        R1 to R3 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio ranges preferably from 0.2:1 to 0.4:1 andpreferably from 0.25:1 to 0.35:1 and more particularly equals 0.3:1.

The weight-average molecular mass (Mw) of these silicones preferablyranges from 2000 to 1 000 000 and more particularly from 3500 to 200000.

According to a third embodiment, the amino silicones corresponding toformula (B) are chosen from the silicones of formula (E) below:

in which:

-   -   p and q are numbers such that the sum (p+q) ranges from 1 to        1000, in particular from 50 to 350 and more particularly from        150 to 250; it being possible for p to denote a number from 0 to        999 and especially from 49 to 349 and more particularly from 159        to 239, and for q to denote a number from 1 to 1000, especially        from 1 to 10 and more particularly from 1 to 5;    -   R1 and R2, which are different, represent a hydroxyl or C₁-C₄        alkoxy radical, at least one of the radicals R1 or R2 denoting        an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio generally ranges from 1:0.8 to 1:1.1 andpreferably from 1:0.9 to 1:1 and more particularly equals 1:0.95.

The weight-average molecular mass (Mw) of the silicone preferably rangesfrom 2000 to 200 000, even more particularly from 5000 to 100 000 andmore particularly from 10 000 to 50 000.

The commercial products comprising silicones of structure (D) or (E) mayinclude in their composition one or more other amino silicones of whichthe structure is different from formula (D) or (E).

A product containing amino silicones of structure (D) is sold by thecompany Wacker under the name Belsil® ADM 652.

A product containing amino silicones of structure (E) is sold by Wackerunder the name Fluid WR 1300®.

When these amino silicones are used, one particularly advantageousembodiment consists in using them in the form of an oil-in-wateremulsion. The oil-in-water emulsion may comprise one or moresurfactants. The surfactants can be of any nature but are preferablycationic and/or non-ionic. The numerical mean size of the siliconeparticles in the emulsion generally ranges from 3 nm to 500 nm.Preferably, especially as amino silicones of formula (E), use is made ofmicroemulsions of which the mean particle size ranges from 5 nm to 60 nm(limits inclusive) and more particularly from 10 nm to 50 nm (limitsinclusive). Thus, use may be made according to the invention of theamino silicone microemulsions of formula (E) sold under the names FinishCT 96 E® or SLM 28020® by the company Wacker.

According to a fourth embodiment, the amino silicones corresponding toformula (B) are chosen from the silicones of formula (F) below:

in which:

-   -   m and n are numbers such that the sum (n+m) ranges from 1 to        2000 and in particular from 50 to 150, it being possible for n        to denote a number from 0 to 1999 and especially from 49 to 149,        and for m to denote a number from 1 to 2000 and especially from        1 to 10;    -   A denotes a linear or branched alkylene radical containing from        4 to 8 carbon atoms and preferably 4 carbon atoms. This radical        is preferably linear.

The weight-average molecular mass (Mw) of these amino siliconespreferably ranges from 2000 to 1 000 000 and even more particularly from3500 to 200 000.

A silicone corresponding to this formula is, for example, the XiameterMEM 8299 Emulsion from Dow Corning.

According to a fifth embodiment, the amino silicones corresponding toformula (B) are chosen from the silicones of formula (G) below:

in which:

-   -   m and n are numbers such that the sum (n+m) ranges from 1 to        2000 and in particular from 50 to 150, it being possible for n        to denote a number from 0 to 1999 and especially from 49 to 149,        and for m to denote a number from 1 to 2000 and especially from        1 to 10;    -   A denotes a linear or branched alkylene radical containing from        4 to 8 carbon atoms and preferably 4 carbon atoms. This radical        is preferably branched.

The weight-average molecular mass (Mw) of these amino siliconespreferably ranges from 500 to 1 000 000 and even more particularly from1000 to 200 000.

A silicone corresponding to this formula is, for example, DC2-8566 AminoFluid from Dow Corning;

c) the amino silicones corresponding to formula (II):

in which:

-   -   R5 represents a monovalent hydrocarbon-based radical containing        from 1 to 18 carbon atoms, and in particular a C₁-C₁₈ alkyl or        C₂-C₁₈ alkenyl radical, for example methyl;    -   R6 represents a divalent hydrocarbon-based radical, especially a        C₁-C₁₈ alkylene radical or a divalent C₁-C₁₈, and for example        C₁-C₈, alkylenoxy radical linked to the Si via an SiC bond;    -   Q- is an anion such as a halide ion, especially chloride, or an        organic acid salt, especially acetate;    -   r represents a mean statistical value ranging from 2 to 20 and        in particular from 2 to 8;    -   s represents a mean statistical value ranging from 20 to 200 and        in particular from 20 to 50.

Such amino silicones are especially described in U.S. Pat. No.4,185,087;

d) the quaternary ammonium silicones of formula (I):

in which:

-   -   R₇, which may be identical or different, represent a monovalent        hydrocarbon-based radical containing from 1 to 18 carbon atoms,        and in particular a C₁-C₁₈ alkyl radical, a C₂-C₁₈ alkenyl        radical or a ring comprising 5 or 6 carbon atoms, for example        methyl;    -   R6 represents a divalent hydrocarbon-based radical, especially a        C₁-C₁₈ alkylene radical or a divalent C₁-C₁₈, and for example        C₁-C₈, alkylenoxy radical linked to the Si via an SiC bond;

R8, which may be identical or different, represent a hydrogen atom, amonovalent hydrocarbon-based radical containing from 1 to 18 carbonatoms, and in particular a C₁-C₁₈ alkyl radical, a C₂-C₁₈ alkenylradical or a radical —R6-NHCOR7;

-   -   X— is an anion such as a halide ion, especially chloride, or an        organic acid salt, especially acetate;    -   r represents a mean statistical value ranging from 2 to 200 and        in particular from 5 to 100.

These silicones are described, for example, in Application EP-A-0 530974;

e) the amino silicones of formula (J):

in which:

-   -   R1, R2, R3 and R4, which may be identical or different, denote a        C₁-C₄ alkyl radical or a phenyl group,    -   R5 denotes a C₁-C₄ alkyl radical or a hydroxyl group,    -   n is an integer ranging from 1 to 5,    -   m is an integer ranging from 1 to 5, and    -   x is chosen such that the amine number ranges from 0.01 to 1        meq/g;

f) the multiblock polyoxyalkylenated amino silicones, of the type (AB)n,A being a polysiloxane block and B being a polyoxyalkylene blockcomprising at least one amine group.

Said silicones preferably are constituted of repeating units of thefollowing general formulae:[—(SiMe2O)xSiMe2-R—N(R″)—R′—O(C₂H₄O)a(C₃H₆O)b—R′—N(H)—R—]or alternatively[—(SiMe2O)xSiMe2-R—N(R″)—R′—O(C₂H₄O)a(C₃H₆O)b-]

in which:

-   -   a is an integer greater than or equal to 1, preferably ranging        from 5 to 200 and more particularly ranging from 10 to 100;    -   b is an integer between 0 and 200, preferably ranging from 4 to        100 and more particularly between 5 and 30;    -   x is an integer ranging from 1 to 10 000 and more particularly        from 10 to 5000;    -   R″ is a hydrogen atom or a methyl;    -   R, which may be identical or different, represent a divalent        linear or branched C₂-C₁₂ hydrocarbon-based radical, optionally        including one or more heteroatoms such as oxygen; preferably, R        denotes an ethylene radical, a linear or branched propylene        radical, a linear or branched butylene radical, or a        —CH₂CH₂CH₂OCH(OH)CH₂— radical; preferentially R denotes a        —CH₂CH₂CH₂OCH(OH)CH₂— radical;    -   R′, which may be identical or different, represent a linear or        branched C₂-C₁₂ divalent hydrocarbon-based radical, optionally        comprising one or more heteroatoms such as oxygen; preferably,        R′ denotes an ethylene radical, a linear or branched propylene        radical, a linear or branched butylene radical, or a        —CH₂CH₂CH₂OCH(OH)CH₂— radical; preferentially, R′ denotes        —CH(CH₃)—CH₂—.

The siloxane blocks preferably represent between 50 mol % and 95 mol %of the total weight of the silicone, more particularly from 70 mol % to85 mol %.

The amine content is preferably between 0.02 and 0.5 meq/g of copolymerin a 30% solution in dipropylene glycol, more particularly between 0.05and 0.2.

The weight-average molecular mass (Mw) of the silicone is preferablybetween 5000 and 1 000 000 and more particularly between 10 000 and 200000.

Mention may be made especially of the silicones sold under the namesSilsoft A-843 or Silsoft A+ by Momentive;

g) and mixtures thereof.

Preferably, the amino silicones are chosen from amino silicones offormula (B), preferentially from the amino silicones of formula (F).

The composition according to the invention may preferably comprise theamino silicone(s) in an amount ranging from 0.01% to 10% by weight,preferably from 0.1% to 5% by weight and better still from 0.5% to 3% byweight, relative to the total weight of the composition.

Surfactants:

The composition according to the present invention may also comprise oneor more surfactants, said surfactants possibly being chosen from anionicsurfactants, amphoteric or zwitterionic surfactants, non-ionicsurfactants and cationic surfactants.

The term “anionic surfactant” is intended to mean a surfactantcomprising as ionic or ionizable groups only anionic groups. Theseanionic groups are preferably chosen from the groups CO₂H, CO₂ ⁻, SO₃H,SO₃ ⁻, OSO₃H, OSO₃ ⁻, H₂PO₃, HPO₃ ⁻, PO₃ ²⁻, H₂PO₂, HPO₂ ⁻, PO₂ ²⁻, POHand PO⁻.

As examples of anionic surfactants that may be used in the compositionaccording to the invention, mention may be made of alkyl sulfates, alkylether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates,monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates,alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates,alkylsulfosuccinates, alkylether sulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates,alkylsulfosuccinamates, acylisethionates and N—(C₁-C₄)alkylN-acyltaurates, salts of alkyl monoesters ofpolyglycoside-polycarboxylic acids, acyllactylates, D-galactoside uronicacid salts, alkyl ether carboxylic acid salts, alkylaryl ethercarboxylic acid salts, alkylamido ether carboxylic acid salts; and thecorresponding non-salified forms of all these compounds; the alkyl andacyl groups of all these compounds (unless otherwise mentioned)generally comprising from 6 to 24 carbon atoms and the aryl groupgenerally denoting a phenyl group.

These compounds may be oxyethylenated and then preferably comprise from1 to 50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylicacids may be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄alkyl polyglycoside-tartrates and C₆-C₂₄ alkylpolyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosen fromalkali metal salts such as the sodium or potassium salt and preferablythe sodium salt, ammonium salts, amine salts and in particular aminoalcohol salts or alkaline-earth metal salts such as the magnesium salt.

Examples of amino alcohol salts that may especially be mentioned includemonoethanolamine, diethanolamine and triethanolamine salts,monoisopropanolamine, diisopropanolamine or triisopropanolamine salts,2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediolsalts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts and in particular the sodiumor magnesium salts are preferably used.

The anionic surfactants that are optionally present may be mild anionicsurfactants, i.e. anionic surfactants without a sulfate function.

Mention may in particular be made, as regards the mild anionicsurfactants, of the following compounds and their salts, and alsomixtures thereof:

polyoxyalkylenated alkyl ether carboxylic acids;

polyoxyalkylenated alkylaryl ether carboxylic acids;

polyoxyalkylenated alkylamido ether carboxylic acids, in particularthose comprising 2 to 50 ethylene oxide groups;

alkyl-D-galactosideuronic acids;

acyl sarcosinates, acyl glutamates; and

alkylpolyglycoside carboxylic esters.

Use may be made most particularly of polyoxyalkylenated carboxylic acidalkyl ethers, for instance carboxylic acid lauryl ether (4.5 OE) sold,for example, under the name Akypo RLM 45 CA from Kao.

The amphoteric or zwitterionic surfactant(s) that may be used in thepresent invention may especially be optionally quaternized secondary ortertiary aliphatic amine derivatives, in which the aliphatic group is alinear or branched chain containing from 8 to 22 carbon atoms, saidamine derivatives containing at least one anionic group, for instance acarboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Mention may be made in particular of (C₈-C₂₀)alkylbetaines,sulfobetaines, (C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines or(C₈-C₂₀)alkylamido(C₆-C₈)-alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic aminederivatives that may be used, as defined above, mention may also be madeof the compounds of respective structures (A₁), (A₂) and (A₃) below:R_(a)—CONHCH₂CH₂—N⁺(R_(b))(R_(c))(CH₂COO⁻)  (A₁)

in which:

R_(a) represents a C₁₀-C₃₀ alkyl or alkenyl group derived from an acidR_(a)—COOH preferably present in hydrolyzed coconut oil, or a heptyl,nonyl or undecyl group,

R_(b) represents a β-hydroxyethyl group, and

R_(c) represents a carboxymethyl group;

andR′_(a)—CONHCH₂CH₂—N(B)(B′)  (A₂)

in which:

B represents —CH₂CH₂OX′,

B′ represents —(CH₂)_(z)—Y′, with z=1 or 2,

X′ represents the —CH₂—COOH, —CH₂—COOZ′, —CH₂CH₂—COOH or —CH₂CH₂—COOZ′group or a hydrogen atom,

Y′ represents —COOH, —COOZ′, or the group —CH₂—CHOH—SO₃H orCH₂—CHOH—SO₃Z′,

Z′ represents an ion resulting from an alkali metal or alkaline-earthmetal, such as sodium, an ammonium ion or an ion resulting from anorganic amine,

R_(a)′ represents a C₁₀-C₃₀ alkyl or alkenyl group of an acidR_(a)′—COOH preferably present in hydrolyzed coconut oil or inhydrolyzed linseed oil, an alkyl group, in particular a C₁₇ alkyl groupand its iso form, or an unsaturated C₁₇ group.

These compounds of formula (A₁) or (A₂) are classified in the CTFAdictionary, 5th edition, 1993, under the names disodiumcocoamphodiacetate, disodium lauroamphodiacetate, disodiumcaprylamphodiacetate, disodium capryloamphodiacetate, disodiumcocoamphodipropionate, disodium lauroamphodipropionate, disodiumcaprylamphodipropionate, disodium capryloamphodipropionate,lauroamphodipropionic acid, cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold bythe company Rhodia under the trade name Miranol® C₂M Concentrate.R_(a)″—NHCH(Y″)—(CH₂)_(n)CONH(CH₂)_(n′)—N(R_(d))(R_(e))  (A₃)

in which formula:

Y″ represents the group —COOH, —COOZ″, —CH₂—CH(OH)SO₃H or the groupCH₂CH(OH)SO₃—Z″;

R_(d) and R_(e), independently of each other, represent a C₁-C₄ alkyl orhydroxyalkyl radical;

Z″ represents a cationic counterion derived from an alkali metal oralkaline-earth metal, such as sodium, an ammonium ion or an ion derivedfrom an organic amine;

R_(a)″ represents a C₁₀-C₃₀ alkyl or alkenyl group of an acidR_(a)″—COOH which is preferably present in hydrolyzed coconut oil or inhydrolyzed linseed oil;

n and n′ denote, independently of each other, an integer ranging from 1to 3.

Among the compounds of formula (A₃), mention may be made of the compoundclassified in the CTFA dictionary under the name sodiumdiethylaminopropyl cocoaspartamide and sold by the company Chimex underthe name Chimexane HB.

Among the abovementioned amphoteric or zwitterionic surfactants, it ispreferred to use (C₈-C₂₀ alkyl)betaines such as cocoylbetaine, (C₈-C₂₀alkyl)amido(C₃-C₈ alkyl)betaines such as cocoylamidopropylbetaine, andmixtures thereof. More preferentially, the amphoteric or zwitterionicsurfactant(s) are chosen from cocoylamidopropylbetaine andcocoylbetaine.

The non-ionic surfactant(s) in the compositions of the present inventionare especially described, for example, in the Handbook of Surfactants byM. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp.116-178. They are especially chosen from fatty alcohols, fatty α-diols,fatty (C₁-C₂₀)alkylphenols and fatty acids, these compounds beingethoxylated, propoxylated or glycerolated and containing at least onefatty chain comprising, for example, from 8 to 18 carbon atoms, thenumber of ethylene oxide or propylene oxide groups possibly rangingespecially from 1 to 200, and the number of glycerol groups possiblyranging especially from 1 to 30.

Mention may also be made of condensates of ethylene oxide and ofpropylene oxide with fatty alcohols, ethoxylated fatty amides preferablyhaving from 1 to 30 ethylene oxide units, polyglycerolated fatty amidescomprising on average from 1 to 5 glycerol groups, and in particularfrom 1.5 to 4, ethoxylated fatty acid esters of sorbitan containing from1 to 30 ethylene oxide units, fatty acid esters of sucrose, fatty acidesters of polyethylene glycol, (C₆-C₂₄ alkyl)polyglycosides,oxyethylenated plant oils, N—(C₆-C₂₄ alkyl)glucamine derivatives, amineoxides such as (C₁₀-C₁₄ alkyl)amine oxides or N—(C₁₀-C₁₄acyl)aminopropylmorpholine oxides.

The cationic surfactant(s) that may be used in the composition accordingto the invention are generally chosen from optionally polyoxyalkylenatedprimary, secondary or tertiary fatty amine salts, quaternary ammoniumsalts, and mixtures thereof.

Mention may in particular be made, as quaternary ammonium salts, forexample, of:

-   -   those corresponding to the general formula (X) below:

in which the groups R₈ to R₁₁, which may be identical or different,represent a linear or branched aliphatic group comprising from 1 to 30carbon atoms or an aromatic group, such as aryl or alkylaryl, at leastone of the groups R₈ to R₁₁ comprising from 8 to 30 carbon atoms andpreferably from 12 to 24 carbon atoms. The aliphatic groups may compriseheteroatoms such as, in particular, oxygen, nitrogen, sulfur andhalogens.

The aliphatic groups are chosen, for example, from C₁-C₃₀ alkyl, C₁-C₃₀alkoxy, polyoxy(C₂-C₆)alkylene, C₁-C₃₀ alkylamide,(C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂-C₂₂)alkyl acetate and C₁-C₃₀hydroxyalkyl groups; X⁻ is an anion chosen from the group of halides,phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates, and(C₁-C₄)alkylsulfonates or (C₁-C₄)alkylarylsulfonates.

Preference is given, among the quaternary ammonium salts of formula (X),on the one hand, to tetraalkylammonium chlorides, such as, for example,dialkyldimethylammonium or alkyltrimethylammonium chlorides in which thealkyl group comprises approximately from 12 to 22 carbon atoms, inparticular behenyltrimethylammonium chloride, distearyldimethylammoniumchloride, cetyltrimethylammonium chloride orbenzyldimethylstearylammonium chloride, or also, on the other hand, todistearoylethylhydroxyethylmethylammonium methosulfate,dipalmitoylethylhydroxyethylammonium methosulfate ordistearoylethylhydroxyethylammonium methosulfate, or also, finally, topalmitylamidopropyltrimethylammonium chloride orstearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold underthe name Ceraphyl® 70 by the company Van Dyk;

-   -   quaternary ammonium salts of imidazoline, for instance those of        formula (XI) below:

in which

R₁₂ represents an alkenyl or alkyl group comprising from 8 to 30 carbonatoms, for example derived from tallow fatty acids,

R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl group or an alkenyl oralkyl group comprising from 8 to 30 carbon atoms,

R₁₄ represents a C₁-C₄ alkyl group,

R₁₅ represents a hydrogen atom, a C₁-C₄ alkyl group, X⁻ is an anionchosen from the group of halides, phosphates, acetates, lactates,(C₁-C₄)alkyl sulfates and (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates.

Preferably, R₁₂ and R₁₃ denote a mixture of alkenyl or alkyl groupscomprising from 12 to 21 carbon atoms, for example derived from tallowfatty acids, R₁₄ denotes a methyl group and R₁₅ denotes a hydrogen atom.Such a product is sold, for example, under the name Rewoquat® W 75 bythe company Rewo;

-   -   quaternary diammonium or triammonium salts, particularly of        formula (XII) below:

in which R₁₆ denotes an alkyl group comprising approximately from 16 to30 carbon atoms, which is optionally hydroxylated and/or interruptedwith one or more oxygen atoms,

R₁₇ is chosen from hydrogen, an alkyl group comprising from 1 to 4carbon atoms or a group —(CH₂)₃—N⁺(R_(16a))(R_(17a))(R_(18a)),

R_(16a), R_(17a), R_(18a), R₁₈, R₁₀, R₂₀ and R₂₁, which may be identicalor different, are chosen from hydrogen or an alkyl group comprising from1 to 4 carbon atoms, and

X⁻ is an anion chosen from the group of halides, acetates, phosphates,nitrates, (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or(C₁-C₄)alkylarylsulfonates, in particular methyl sulfate and ethylsulfate.

Such compounds are, for example, Finquat CT-P, available from Finetex(Quaternium 89), and Finquat CT, available from Finetex (Quaternium 75);

-   -   quaternary ammonium salts comprising one or more ester        functional groups, such as those of formula (XIII) below:

in which:

R₂₂ is chosen from C₁-C₆ alkyl groups and C₁-C₆ hydroxyalkyl ordihydroxyalkyl groups,

R₂₃ is chosen from:

-   -   the group

-   -   saturated or unsaturated, linear or branched C₁-C₂₂        hydrocarbon-based groups R₂₇,    -   a hydrogen atom,

R₂₅ is chosen from:

-   -   the group

-   -   saturated or unsaturated, linear or branched C₁-C₆        hydrocarbon-based groups R₂₉,    -   a hydrogen atom,

R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen fromsaturated or unsaturated, linear or branched C₇-C₂₁ hydrocarbon-basedgroups;

r, s and t, which may be identical or different, are integers rangingfrom 2 to 6,

r1 and t1, which are identical or different, have the values 0 or 1,

r2+r1=2 r and t1+t2=2 t,

y is an integer ranging from 1 to 10,

x and z, which may be identical or different, are integers having valuesfrom 0 to 10,

X⁻ is a simple or complex, organic or inorganic anion,

with the proviso that the sum x+y+z is from 1 to 15, that when x is 0then R₂₃ denotes R₂₇, and that when z is 0 then R₂₅ denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularlylinear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropylgroup, and more particularly a methyl or ethyl group.

Advantageously, the sum x+y+z is from 1 to 10.

When R₂₃ is an R₂₇ hydrocarbon-based group, it can be long and have from12 to 22 carbon atoms or be short and have from 1 to 3 carbon atoms.

When R₂₅ is a hydrocarbon-based group R₂₉, it preferably contains 1 to 3carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂₈, which may be identical or different,are chosen from linear or branched, saturated or unsaturated C₁₁-C₂₁hydrocarbon-based groups, and more particularly from linear or branched,saturated or unsaturated C₁₁-C₂₁ alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, have the value0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, have thevalue 2 or 3 and more particularly still are equal to 2.

The anion X⁻ is preferably a halide, preferably chloride, bromide oriodide, a (C₁-C₄)alkyl sulfate, or a (C₁-C₄)alkylsulfonate or(C₁-C₄)alkylarylsulfonate. However, use may be made of methanesulfonate,phosphate, nitrate, tosylate, an anion derived from an organic acid,such as acetate or lactate, or any other anion which is compatible withthe ammonium having an ester function.

The anion X⁻ is more particularly still chloride, methyl sulfate orethyl sulfate.

Use is made more particularly, in the composition according to theinvention, of the ammonium salts of formula (XIII) in which:

-   -   R₂₂ denotes a methyl or ethyl group,    -   x and y are equal to 1,    -   z is equal to 0 or 1,    -   r, s and t are equal to 2,    -   R₂₃ is chosen from:    -   the group

-   -   methyl, ethyl or C₁₄-C₂₂ hydrocarbon groups,    -   a hydrogen atom,    -   R₂₅ is chosen from:    -   the group

-   -   a hydrogen atom,    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are        chosen from linear or branched, saturated or unsaturated C₁₃-C₁₇        hydrocarbon-based groups, and preferably from linear or        branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl        groups.

Advantageously, the hydrocarbon-based groups are linear.

Among the compounds of formula (XIII), examples that may be mentionedinclude salts, especially the chloride or methyl sulfate, ofdiacyloxyethyldimethylammonium,diacyloxyethylhydroxyethylmethylammonium,monoacyloxyethyldihydroxyethylmethylammonium,triacyloxyethylmethylammonium ormonoacyloxyethylhydroxyethyldimethyl-ammonium, and mixtures thereof. Theacyl groups preferably contain 14 to 18 carbon atoms and are obtainedmore particularly from a plant oil such as palm oil or sunflower oil.When the compound contains several acyl groups, these groups may beidentical or different.

These products are obtained, for example, by direct esterification oftriethanolamine, triisopropanolamine, alkyldiethanolamine oralkyldiisopropanolamine, which are optionally oxyalkylenated, with fattyacids or with fatty acid mixtures of plant or animal origin, or bytransesterification of the methyl esters thereof. This esterification isfollowed by a quaternization by means of an alkylating agent such as analkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate,preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methylpara-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by thecompany Henkel, Stepanquat® by the company Stepan, Noxamium® by thecompany CECA or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, amixture of quaternary ammonium monoester, diester and triester saltswith a majority by weight of diester salts.

It is also possible to use the ammonium salts containing at least oneester function that are described in U.S. Pat. Nos. 4,874,554 and4,137,180.

Use may also be made of behenoylhydroxypropyltrimethylammonium chloridesold by the company Kao under the name Quartamin BTC 131, for example.

Preferably, the ammonium salts containing at least one ester functioncontain two ester functions.

Among the cationic surfactants, it is more particularly preferred tochoose cetyltrimethylammonium, behenyltrimethylammonium anddipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof,and more particularly behenyltrimethylammonium chloride,cetyltrimethylammonium chloride, anddipalmitoylethylhydroxyethylmethylammonium methosulfate, and mixturesthereof.

Preferably, the surfactant(s) is(are) chosen from cationic or non-ionicsurfactants, and mixtures thereof, preferably cationic surfactants.

When the composition comprises one or more surfactants, their contentmay preferably range from 0.05% to 20% by weight, more preferentiallyfrom 0.1% to 10% by weight and better still from 0.5% to 5% by weightrelative to the total weight of the composition.

The composition preferably comprises one or more cationic surfactants ina content ranging from 0.05% to 20% by weight, more preferentially from0.1% to 10% by weight and better still from 0.5% to 5% by weightrelative to the total weight of the composition.

Thickening Polymers

The composition may also comprise one or more thickening polymers.

This thickening polymer is chosen from ionic or non-ionic,non-associative polymers, or from non-ionic, anionic, cationic oramphoteric, associative polymers, and also mixtures thereof.

For the purpose of the present invention, the term “thickening polymer”is intended to mean a polymer which, when introduced at 1% in a pureaqueous solution or an aqueous-alcoholic solution containing 30%ethanol, and at pH=7, makes it possible to achieve a viscosity of atleast 100 cps and preferably of at least 500 cps, at 25° C. and at ashear rate of 1 s⁻¹. This viscosity can be measured using a cone/plateviscometer (Haake R600 rheometer or the like). Preferably, thesepolymers increase, through their presence, the viscosity of thecompositions into which they are introduced by at least 50 cps andpreferably 200 cps, at 25° C. and at a shear rate of 1 s⁻¹.

As regards the non-associative thickening polymers, it is first recalledthat, for the purposes of the present invention, non-associativethickening polymers are thickening polymers not containing any C₈-C₃₀fatty chains.

Among the non-associative thickening polymers present, mention may bemade of:

a) crosslinked acrylic or methacrylic acid homopolymers or copolymers,

b) crosslinked homopolymers of 2-acrylamido-2-methylpropanesulfonicacid, and crosslinked acrylamide copolymers thereof,

c) ammonium acrylate homopolymers or copolymers of ammonium acrylate andof acrylamide,

d) non-ionic guar gums,

e) gums of biopolysaccharides of microbial origin, gums derived fromplant exudates,

f) celluloses, in particular hydroxyethyl-, hydroxypropyl- orcarboxymethylcelluloses,

g) pectins and alginates,

h) mixtures thereof.

A first family of non-associative thickening polymers that is suitableis represented by crosslinked acrylic acid homopolymers, such as thosecrosslinked by an allyl ether of an alcohol from the sugar series, suchas, for example, the products sold under the names Carbopol 980, 981,954, 2984 and 5984 by the company Noveon or the products sold under thenames Synthalen M and Synthalen K by the company 3 VSA.

The non-associative thickening polymers may also be crosslinked(meth)acrylic acid copolymers, such as the polymer sold under the nameAqua SF1 by the company Noveon.

The non-associative thickening polymers may be chosen from crosslinked2-acrylamido-2-methylpropanesulfonic acid homopolymers and thecrosslinked acrylamide copolymers thereof.

As regards these homopolymers and copolymers, which may be partially ortotally neutralized, mention may be made of polymers comprising from 90%to 99.9% by weight, relative to the total weight of the polymer, ofunits of formula (j) below:

in which X⁺ denotes a cation or a mixture of cations, or a proton.

More particularly, the cations are chosen from alkali metals (forinstance sodium or potassium), ammonium ions optionally substituted with1 to 3 alkyl radicals, which may be identical or different, containingfrom 1 to 6 carbon atoms, optionally bearing at least one hydroxylradical, cations derived from N-methylglucamine or from basic aminoacids, for instance arginine and lysine.

Preferably, the cation is an ammonium or sodium ion. Moreover, thepolymer comprises from 0.01% to 10% by weight, relative to the totalweight of the polymer, of crosslinking units derived from at least onemonomer containing at least two ethylenic unsaturations (carbon-carbondouble bond).

The crosslinking monomers containing at least two ethylenicunsaturations are chosen, for example, from diallyl ether, triallylcyanurate, diallyl maleate, allyl (meth)acrylate, dipropylene glycoldiallyl ether, polyglycol diallyl ethers, triethylene glycol divinylether, hydroquinone diallyl ether, tetraallyloxyethanoyl, tetra- ordiethylene glycol di(meth)acrylate, triallylamine,tetraallylethylenediamine, trimethylolpropane diallyl ether,trimethylolpropane triacrylate, methylenebis(meth)acrylamide ordivinylbenzene, allylic ethers of alcohols of the sugar series, or otherallylic or vinyl ethers of polyfunctional alcohols, and also allylicesters of phosphoric and/or vinylphosphonic acid derivatives, ormixtures of these compounds.

For further details regarding these polymers, reference may be made todocument EP 815 828.

Among the partially or totally neutralized crosslinked copolymers of2-acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention maybe made in particular of the product described in Example 1 of documentEP 503 853, and reference may be made to said document as regards thesepolymers.

The composition may similarly comprise, as non-associative thickeningpolymers, ammonium acrylate homopolymers or copolymers of ammoniumacrylate and of acrylamide.

Among the ammonium acrylate homopolymers that may be mentioned by way ofexample is the product sold under the name Microsap PAS 5193 by thecompany Hoechst. Among the copolymers of ammonium acrylate and ofacrylamide that may be mentioned is the product sold under the nameBozepol C Nouveau or the product PAS 5193 sold by the company Hoechst.Reference may be made especially to documents FR 2 416 723, U.S. Pat.Nos. 2,798,053 and 2,923,692 as regards the description and preparationof such compounds.

The composition may also comprise dimethylaminoethyl methacrylatehomopolymers quaternized with methyl chloride or dimethylaminoethylmethacrylate copolymers quaternized with methyl chloride and acrylamide.

Among the homopolymers of this type, mention may be made of the productssold under the names Salcare SC95 and Salcare SC96 by the company Ciba.

Among the copolymers of this family, mention may be made of the productSalcare SC92 sold by Ciba or the product PAS 5194 sold by Hoechst. Thesepolymers are especially described and prepared in document EP 395 282,to which reference may be made.

By way of non-associative thickening polymers, mention may be made ofnon-ionic guar gums, for instance the non-modified, non-ionic guar gumssold under the name Vidogum GH 175 by the company Uni Pectin and underthe name Jaguar C by the company Meyhall.

The non-ionic guar gums that may be used according to the invention arepreferably modified with C₁-C₆ hydroxyalkyl groups. Among thehydroxyalkyl groups that may be mentioned, for example, arehydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and may be prepared, forexample, by reacting the corresponding alkene oxides, for instance,propylene oxides, with the guar gum so as to obtain a guar gum modifiedwith hydroxypropyl groups.

The degree of hydroxyalkylation, which corresponds to the number ofalkylene oxide molecules consumed by the number of free hydroxylfunctions present on the guar gum, preferably ranges from 0.4 to 1.2.

Such non-ionic guar gums optionally modified with hydroxyalkyl groupsare sold, for example, under the trade names Jaguar HP8, Jaguar HP60 andJaguar HP120, Jaguar DC 293 and Jaguar HP 105 by the company Meyhall orunder the name Galactasol 4H4FD2 by the company Aqualon.

By way of suitable non-associative thickening polymers, mention may alsobe made of biopolysaccharide gums of microbial origin, such asscleroglucan or xanthan gums.

Also suitable are gums derived from plant exudates, such as gum arabic,gum ghatti, karaya and tragacanth gums; celluloses, in particularhydroxyethyl-, hydroxypropyl- or carboxymethylcelluloses; pectines andalginates.

These polymers are well known to those skilled in the art and are inparticular described in the book by Robert L. Davidson entitled“Handbook of Water soluble gums and resins” published by Mc Graw HillBook Company (1980).

It is recalled that associative polymers are hydrophilic polymers thatare capable, in an aqueous medium, of reversibly associating with eachother or with other molecules.

Their chemical structure more particularly comprises at least onehydrophilic region and at least one hydrophobic region.

The term “hydrophobic group” is intended to mean a radical or polymerwith a saturated or unsaturated, linear or branched hydrocarbon-basedchain, comprising at least 8 carbon atoms, preferably from 10 to 30carbon atoms, in particular from 12 to 30 carbon atoms and morepreferentially from 18 to 30 carbon atoms.

Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may bederived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol ordecyl alcohol. It may also denote a hydrocarbon-based polymer, such as,for example, polybutadiene.

Among the associative polymers suitable for implementing the invention,mention may be made of:

a) anionic associative polymers comprising at least one hydrophilic unitof the type of an ethylenic unsaturated anionic monomer, in particularcarboxyvinylic acid, and most particularly an acrylic acid or amethacrylic acid or mixtures thereof, and at least one fatty-chain allylether unit comprising from 8 to 30 carbon atoms, in particularcorresponding to the monomer of formula (I) below:CH₂═C R′CH₂O B_(n),R  (I)

in which R′ denotes H or CH₃, B denotes an ethylenoxy radical, n is zeroor denotes an integer ranging from 1 to 100, R denotes ahydrocarbon-based radical chosen from alkyl, arylalkyl, aryl, alkylaryland cycloalkyl radicals, containing from 8 to 30 carbon atoms,preferably 10 to 24 carbon atoms and even more particularly from 12 to18 carbon atoms. A unit of formula (I) that is more particularlypreferred is a unit in which R′ denotes H, n is equal to 10, and Rdenotes a stearyl radical (C18).

Anionic associative polymers of this type are described and prepared,according to an emulsion polymerization process in Patent EP-0 216 479.

Among these anionic associative polymers, those that are particularlypreferred according to the invention are polymers formed from 20% to 60%by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% byweight of lower alkyl (meth)acrylates, from 2% to 50% by weight offatty-chain allyl ether of formula (I), and from 0 to 1% by weight of acrosslinking agent which is a well-known copolymerizable unsaturatedpolyethylenic monomer, for instance diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate ormethylenebisacrylamide. Among the latter polymers, those mostparticularly preferred are crosslinked terpolymers of methacrylic acid,of ethyl acrylate and of polyethylene glycol (10 OE) stearyl alcoholether (Steareth-10), especially those sold by the company Ciba under thenames Salcare SC800 and Salcare SC900, which are aqueous 30% emulsionsof a crosslinked terpolymer of methacrylic acid, of ethyl acrylate andof steareth-10 allyl ether (40/50/10);

b) anionic associative polymers comprising at least one hydrophilic unitof unsaturated olefinic carboxylic acid type, and at least onehydrophobic unit of the type such as a (C₁₀-C₃₀) alkyl ester of anunsaturated carboxylic acid. These polymers are preferably chosen fromthose for which the hydrophilic unit of unsaturated olefinic carboxylicacid type corresponds to the monomer of formula (II) below:

in which R1 denotes H or CH₃ or C₂H₅, i.e. acrylic acid, methacrylicacid or ethacrylic acid units, and of which the hydrophobic unit of thetype such as a (C₁₀-C₃₀) alkyl ester of an unsaturated carboxylic acidcorresponds to the monomer of formula (III) below:

in which R2 denotes H or CH₃ or C₂H₅ (i.e. acrylate, methacrylate orethacrylate units) and preferably H (acrylate units) or CH₃(methacrylate units), R3 denoting a C₁₀-C₃₀ and preferably C₁₂-C₂₂ alkylradical.

(C₁₀-C₃₀) alkyl esters of unsaturated carboxylic acids in accordancewith the invention comprise, for example, lauryl acrylate, stearylacrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, andthe corresponding methacrylates, lauryl methacrylate, stearylmethacrylate, decyl methacrylate, isodecyl methacrylate and dodecylmethacrylate.

Anionic polymers of this type are described and prepared, for example,according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

Use will more particularly be made, among anionic associative polymersof this type, of polymers formed from a mixture of monomers comprising:

-   -   essentially acrylic acid,    -   an ester of formula (III) described above and in which R2        denotes H or CH₃, R3 denoting an alkyl radical containing from        12 to 22 carbon atoms, and    -   a crosslinking agent, which is a well-known copolymerizable        unsaturated polyethylenic monomer, for instance diallyl        phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene        glycol dimethacrylate and methylenebisacrylamide.

Among the anionic associative polymers of this type, use will be mademore particularly of those formed from 95% to 60% by weight of acrylicacid (hydrophilic unit), 4% to 40% by weight of C₁₀-C₃₀ alkyl acrylate(hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizablemonomer, or alternatively those formed from 98% to 96% by weight ofacrylic acid (hydrophilic unit), 1% to 4% by weight of C₁₀-C₃₀ alkylacrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinkingpolymerizable monomer such as those described previously.

Among said polymers above, preference is very particularly given,according to the present invention, to the products sold by the companyGoodrich under the trade names Pemulen TR1®, Pemulen TR2® and Carbopol1382®, and even more preferentially Pemulen TR1®, and to the productsold by the company SEPPIC under the name Coatex SX®.

Mention may also be made of polymers which, besides the monomers offormula (II) and of formula (III), contain one or more other monomers.This additional monomer may especially be a vinyllactam and inparticular vinylpyrrolidone.

An example of a polymer that may be mentioned is the acrylic acid/laurylmethacrylate/vinylpyrrolidone terpolymer sold under the name AcrylidoneLM by the company ISP;

-   -   (c) maleic anhydride/C₃₀-C₃₈ alpha-olefin/alkyl maleate anionic        associative terpolymers, such as the product (maleic        anhydride/C₃₀-C₃₈ alpha-olefin/isopropyl maleate copolymer) sold        under the name Performa V 1608® by the company Newphase        Technologies;

d) acrylic anionic associative terpolymers comprising:

(i) 20% to 70% by weight of an α,β-monoethylenically unsaturatedcarboxylic acid,

(ii) 20% to 80% by weight of a non-surfactant, α,β-monoethylenicallyunsaturated monomer other than (i),

(iii) 0.5% to 60% by weight of a non-ionic monourethane which is theproduct of reaction of a monohydric surfactant with a monoethylenicallyunsaturated monoisocyanate,

such as those described in patent application EP-A-0 173 109 and moreparticularly the terpolymer described in Example 3, namely a methacrylicacid/methyl acrylate/behenyl alcoholdimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 OE)terpolymer, as an aqueous 25% dispersion;

e) anionic associative copolymers comprising, among their monomers, acarboxylic acid having α,β-monoethylenic unsaturation and an ester ofcarboxylic acid having α,β-monoethylenic unsaturation and of anoxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of anα,β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄alcohol.

By way of example of this type of compound, mention may be made ofAculyn® 22 sold by the company Rohm and Haas, which is an oxyalkylenatedmethacrylic acid/ethyl acrylate/stearyl methacrylate terpolymer;

f) associative celluloses modified with groups comprising at least 30one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprisingfrom 8 to 30 carbon atoms;

g) quaternized hydroxyethylcelluloses modified with groups comprising atleast one fatty chain, such as alkyl, arylalkyl or alkylaryl groupscomprising from 8 to 30 carbon atoms.

The alkyl radicals borne by the above quaternized celluloses orhydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms.The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthrylgroups.

Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃₀fatty chains that may be indicated include the products Quatrisoft LM200®, Quatrisoft LM-X529-18-A®, Quatrisoft LM-X529-18B® (C₁₂ alkyl) andQuatrisoft LM-X529-8® (C₁₈ alkyl) sold by the company Amerchol and theproducts Crodacel QM®, Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (C₁₈alkyl) sold by the company Croda;

(h) the cationic polymer(s) obtained by polymerization of a monomermixture comprising one or more vinyl monomers substituted with one ormore amino groups, one or more hydrophobic non-ionic vinyl monomers, andone or more associative vinyl monomers.

In particular, among these cationic polymers, mention may be madeespecially of the compound sold by the company Noveon under the nameAqua CC and which corresponds to the INCI name Polyacrylate-1Crosspolymer. Polyacrylate-1 Crosspolymer is the product ofpolymerization of a monomer mixture comprising:

-   -   a di(C₁-C₄ alkyl)amino(C₁-C₆ alkyl) methacrylate,    -   one or more C₁-C₃₀ alkyl esters of (meth)acrylic acid,    -   a polyethoxylated C₁₀-C₃₀ alkyl methacrylate (20-25 mol of        ethylene oxide units),    -   a 30/5 polyethylene glycol/polypropylene glycol allyl ether,    -   a hydroxy(C₂-C₈ alkyl) methacrylate, and    -   an ethylene glycol dimethacrylate;

i) the amphoteric associative polymers prepared by copolymerizing: 1) atleast one monomer of formula (Ibis) or (IIbis) below:

in which R1 and R2, which may be identical or different, represent ahydrogen atom or a methyl radical, R3, R4 and R5, which may be identicalor different, represent a linear or branched alkyl radical containingfrom 1 to 30 carbon atoms,

Z represents an NH group or an oxygen atom,

n is an integer from 2 to 5,

A⁻ is an anion derived from an organic or mineral acid, such as amethosulfate anion or a halide such as chloride or bromide;

2) at least one monomer of formula (IIIbis):

in which R6 and R7, which may be identical or different, represent ahydrogen atom or a methyl radical; and

3) at least one monomer of formula (IVbis):

in which R6 and R7, which may be identical or different, represent ahydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atomand R8 denotes a linear or branched alkyl radical containing from 1 to30 carbon atoms; at least one of the monomers of formula (Ibis), (IIbis)or (IIIbis) comprising at least one fatty chain comprising 8 to 30carbon atoms.

The monomers of formulae (Ibis) and (IIbis) of the present invention arepreferably chosen from the group constituted of:

-   -   dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,    -   diethylaminoethyl methacrylate, diethylaminoethyl acrylate,    -   dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,    -   dimethylaminopropylmethacrylamide,        dimethylaminopropylacrylamide,

these monomers optionally being quaternized, for example with a C₁-C₄alkyl halide or a C₁-C₄ dialkyl sulfate.

More particularly, the monomer of formula (Ibis) is chosen fromacrylamidopropyltrimethylammonium chloride andmethacrylamidopropyltrimethylammonium chloride.

The monomers of formula (IIIbis) of the present invention are preferablychosen from the group constituted of acrylic acid, methacrylic acid,crotonic acid and 2-methylcrotonic acid. More particularly, the monomerof formula (VII) is acrylic acid.

The monomers of formula (IV) of the present invention are preferablychosen from the group constituted of C₁₂-C₂₂ and more particularlyC₁₆-C₁₈ alkyl acrylates or methacrylates.

The monomers constituting the fatty-chain amphoteric polymers of theinvention are preferably already neutralized and/or quaternized.

The ratio of the number of cationic charges/anionic charges ispreferably equal to about 1.

The amphoteric associative polymers according to the inventionpreferably comprise from 1 mol % to 10 mol % of the monomer comprising afatty chain (monomer of formula (Ibis), (IIbis) or (IVbis)), andpreferably from 1.5 mol % to 6 mol %.

The weight-average molecular weights of the amphoteric associativepolymers according to the invention may range from 500 to 50 000 000 andare preferably between 10 000 and 5 000 000.

The amphoteric associative polymers according to the invention may alsocontain other monomers such as non-ionic monomers and in particular suchas C₁-C₄ alkyl acrylates or methacrylates.

Amphoteric associative polymers according to the invention are describedand prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention,the ones that are preferred are acrylicacid/(meth)acrylamidopropyltrimethylammonium chloride/stearylmethacrylate terpolymers;

j) non-ionic associative celluloses modified with groups comprising atleast one fatty chain comprising from 8 to 30 carbon atoms andpreferably from 10 to 22 carbon atoms, such as alkyl, arylalkyl oralkylaryl groups, or mixtures thereof, and in which the alkyl groups arepreferably C₈-C₂₂, for instance the product Natrosol Plus Grade 330 CS®(C₁₆ alkyl) sold by the company Aqualon, or the product Bermocoll EHM100® sold by the company Berol Nobel.

Also suitable are those modified with alkylphenyl polyalkylene glycolether groups, such as the product Amercell Polymer HM-1500® (nonylphenylpolyethylene glycol (15) ether) sold by the company Amerchol;

k) associative non-ionic hydroxypropyl guars modified with groupscomprising at least one fatty chain comprising from 8 to 30 carbon atomsand preferably from 10 to 22 carbon atoms, such as the product EsaflorHM 22® (C₂₂ alkyl chain) sold by the company Lamberti, and the productsRE210-18® (C₁₄ alkyl chain) and RE205-1® (C₂₀ alkyl chain) sold by thecompany Rhodia;

l) associative non-ionic copolymers of vinylpyrrolidone and ofhydrophobic monomers comprising a fatty chain comprising from 8 to 30carbon atoms and preferably from 10 to 22 carbon atoms, of which mentionmay, by way of example, be made of:

-   -   the products Antaron V216® or Ganex V216®        (vinylpyrrolidone/hexadecene copolymer), sold by the company        ISP,    -   the products Antaron V220® or Ganex V220®        (vinylpyrrolidone/eicosene copolymer), sold by the company ISP;

m) associative non-ionic copolymers of C₁-C₆ alkyl methacrylates oracrylates and of amphiphilic monomers comprising at least one fattychain comprising from 8 to 30 carbon atoms and preferably from 10 to 22carbon atoms, which are preferably oxyethylenated, for instance theoxyethylenated methyl acrylate/stearyl acrylate copolymer sold by thecompany Goldschmidt under the name Antil 208®;

n) associative non-ionic copolymers of hydrophilic methacrylates oracrylates and of hydrophobic monomers comprising at least one fattychain comprising from 8 to 30 carbon atoms and preferably from 10 to 22carbon atoms, for instance the polyethylene glycol methacrylate/laurylmethacrylate copolymer;

o) associative non-ionic polyether polyurethanes comprising, in theirchain, both hydrophilic blocks, which are preferably polyoxyethylenated,and hydrophobic blocks which may be aliphatic sequences alone and/orcycloaliphatic and/or aromatic sequences comprising from 8 to 30 carbonatoms and preferably from 10 to 22 carbon atoms;

p) associative non-ionic polymers with an aminoplast ether backbonehaving at least one fatty chain comprising from 8 to 30 carbon atoms andpreferably from 10 to 22 carbon atoms, such as the compounds Pure Thix®provided by the company Sud-Chemie;

q) mixtures thereof.

Preferably, the thickening polymer(s) are chosen from celluloses, inparticular hydroxyethyl-, hydroxypropyl- or carboxymethylcelluloses.

Advantageously, the content of thickening polymer ranges from 0.01% to10% by weight, preferably from 0.1% to 5% by weight and better stillfrom 0.2% to 3% by weight relative to the total weight of thecomposition. Alkaline agent:

Cationic Polymer

The cosmetic composition may also comprise one or more cationicpolymers.

For the purposes of the present invention, the term “cationic polymer”denotes any polymer containing cationic groups and/or groups that can beionized into cationic groups.

The cationic polymers that may be present in the composition accordingto the invention may be chosen from any of those already known per se asimproving the cosmetic properties of the hair, i.e. especially thosedescribed in patent application EP-A-337 354 and in French patents FR-2270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

The cationic polymers that are preferred are chosen from thosecontaining units comprising primary, secondary, tertiary and/orquaternary amine groups, which may either form part of the main polymerchain or be carried by a side substituent directly attached thereto.

The cationic polymers used generally have a number-average molecularmass of between 500 and 5×10⁶ approximately and preferably between 10³and 3×10⁶ approximately.

Among the cationic polymers, mention may more particularly be made ofpolymers of the polyamine, polyaminoamide and polyquaternary ammoniumtype.

These are known products. They are especially described in Frenchpatents 2 505 348 and 2 542 997. Among said polymers, mention may bemade of:

(1) homopolymers or copolymers derived from acrylic or methacrylicesters or amides and comprising at least one of the units of formula(IX), (X), (XI) or (XII) below:

in which:

R3, which may be identical or different, denote a hydrogen atom or a CH₃radical;

A, which may be identical or different, represent a linear or branchedalkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or ahydroxyalkyl group of 1 to 4 carbon atoms;

R₄, R₅ and R₆, which may be identical or different, represent an alkylgroup containing from 1 to 18 carbon atoms or a benzyl radical andpreferably an alkyl group containing from 1 to 6 carbon atoms;

R₁ and R₂, which may be identical or different, represent hydrogen or analkyl group containing from 1 to 6 carbon atoms, and preferably methylor ethyl;

X denotes an anion derived from a mineral or organic acid, such as amethosulfate anion or a halide such as chloride or bromide.

Mention may be made in particular of the ethyltrimethylammoniummethacrylate chloride homopolymer.

The polymers of family (1) can also contain one or more units derivedfrom comonomers which may be chosen from the family of acrylamides,methacrylamides, diacetone acrylamides, acrylamides and methacrylamidessubstituted on the nitrogen with lower (C₁-C₄) alkyls, acrylic ormethacrylic acids or esters thereof, vinyllactams such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these polymers of family (1), mention may be made of:

-   -   copolymers of acrylamide and of dimethylaminoethyl methacrylate        quaternized with dimethyl sulfate or with a dimethyl halide,        such as the product sold under the name Hercofloc by the company        Hercules,    -   the copolymers of acrylamide and of        methacryloyloxyethyltrimethylammonium chloride described, for        example, in patent application EP-A-080 976 and sold under the        name Bina Quat P 100 by the company Ciba Geigy,    -   the copolymer of acrylamide and of        methacryloyloxyethyltrimethylammonium methosulfate sold under        the name Reten by the company Hercules,    -   quaternized or non-quaternized        vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate        copolymers, such as the products sold under the name Gafquat by        the company ISP, such as, for example, Gafquat 734 or Gafquat        755, or alternatively the products known as Copolymer 845, 958        and 937. These polymers are described in detail in French        patents 2 077 143 and 2 393 573,    -   dimethylaminoethyl        methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such        as the product sold under the name Gaffix VC 713 by the company        ISP,    -   vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers        sold in particular under the name Styleze CC 10 by ISP,    -   quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide        copolymers such as the product sold under the name Gafquat HS        100 by the company ISP,    -   the crosslinked polymers of        methacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium salts, such        as the polymers obtained by homopolymerization of        dimethylaminoethyl methacrylate quaternized with methyl        chloride, or by copolymerization of acrylamide with        dimethylaminoethyl methacrylate quaternized with methyl        chloride, the homopolymerization or copolymerization being        followed by crosslinking with an olefinically unsaturated        compound, in particular methylenebisacrylamide. Use may more        particularly be made of a crosslinked        acrylamide/methacryloyloxyethyltrimethylammonium chloride        copolymer (20/80 by weight) in the form of a dispersion        containing 50% by weight of said copolymer in mineral oil. This        dispersion is sold under the name Salcare® SC 92 by the company        Ciba. Use may also be made of a crosslinked homopolymer of        methacryloyloxyethyltrimethylammonium chloride containing        approximately 50% by weight of the homopolymer in mineral oil or        in a liquid ester. These dispersions are sold under the names        Salcare® SC 95 and Salcare® SC 96 by the company Ciba;

(2) the cellulose ether derivatives containing quaternary ammoniumgroups, described in French patent 1 492 597, and in particular thepolymers sold under the names Ucare Polymer “JR” (JR 400 LT, JR 125 andJR 30M) or “LR” (LR 400 or LR 30M) by the company Amerchol. Thesepolymers are also defined in the CTFA dictionary as quaternary ammoniumsof hydroxyethylcellulose that have reacted with an epoxide substitutedwith a trimethylammonium group;

(3) cellulose copolymers or cellulose derivatives grafted with awater-soluble quaternary ammonium monomer, and described especially inU.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instancehydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, inparticular, with a methacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The commercial products corresponding to this definition are moreparticularly the products sold under the names Celquat L 200 and CelquatH 100 by the company National Starch;

(4) the cationic guar gums described more particularly in U.S. Pat. No.3,589,578 and 4 031 307, such as guar gums containing cationictrialkylammonium groups. Guar gums modified with a2,3-epoxypropyltrimethylammonium salt (e.g. chloride) are used, forexample.

Such products are sold in particular under the trade names Jaguar C13 S,Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Rhodia;

(5) polymers constituted of piperazinyl units and of divalent alkyleneor hydroxyalkylene radicals containing straight or branched chains,optionally interrupted with oxygen, sulfur or nitrogen atoms or byaromatic or heterocyclic rings, and also the oxidation and/orquaternization products of these polymers. Such polymers are described,in particular, in French patents 2 162 025 and 2 280 361;

(6) water-soluble polyaminoamides prepared in particular bypolycondensation of an acid compound with a polyamine; thesepolyaminoamides can be crosslinked by an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, abis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkylhalide or alternatively by an oligomer resulting from the reaction of adifunctional compound which is reactive with regard to a bis-halohydrin,a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, anepihalohydrin, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in proportions ranging from 0.025 to 0.35mol per amine group of the polyaminoamide; these polyaminoamides can bealkylated or, if they contain one or more tertiary amine functionalgroups, quaternized. Such polymers are especially described in Frenchpatents 2 252 840 and 2 368 508;

(7)polyaminoamide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationwith difunctional agents. Mention may be made, for example, of adipicacid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which thealkyl radical contains from 1 to 4 carbon atoms and preferably denotesmethyl, ethyl or propyl. Such polymers are in particular described inFrench patent 1 583 363.

Among these derivatives, mention may be made more particularly of theadipic acid/dimethylamino-hydroxy-propyl/diethylenetriamine polymerssold under the name Cartaretine F, F4 or F8 by the company Sandoz;

(8) polymers obtained by reaction of a polyalkylene polyamine containingtwo primary amine groups and at least one secondary amine group with adicarboxylic acid chosen from diglycolic acid and saturated aliphaticdicarboxylic acids containing from 3 to 8 carbon atoms. The mole ratiobetween the polyalkylene polyamine and the dicarboxylic acid is between0.8:1 and 1.4:1; the polyaminoamide resulting therefrom is reacted withepichlorohydrin in a mole ratio of epichlorohydrin relative to thesecondary amine group of the polyaminoamide of between 0.5:1 and 1.8:1.Such polymers are described in particular in U.S. Pat. Nos. 3,227,615and 2,961,347.

Polymers of this type are sold in particular under the name Hercosett 57by Hercules Inc. or else under the name PD 170 or Delsette 101 byHercules in the case of the adipic acid/epoxypropyl/diethylenetriaminecopolymer;

(9) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium,such as homopolymers or copolymers comprising, as main constituent ofthe chain, units corresponding to formula (XIII) or (XIV):

in which formulae k and t are equal to 0 or 1, the sum k+t being equalto 1; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈,independently of each other, denote an alkyl group containing from 1 to6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferablycontains 1 to 5 carbon atoms, or a lower (C₁-C₄) amidoalkyl group, or R₇and R₈ may denote, together with the nitrogen atom to which they areattached, heterocyclic groups, such as piperidyl or morpholinyl; R₇ andR₈, independently of each other, preferably denote an alkyl groupcontaining from 1 to 4 carbon atoms; Y⁻ is an anion such as bromide,chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite,sulfate or phosphate. These polymers are in particular described inFrench patent 2 080 759 and in its Certificate of Addition 2 190 406.

Among the polymers defined above, mention may be made more particularlyof the dimethyldiallylammonium chloride homopolymer sold under the nameMerquat 100 by the company Nalco (and its homologues of lowweight-average molecular mass) and the copolymers ofdiallyldimethylammonium chloride and of acrylamide, sold under the namesMerquat 550 and Merquat 7SPR;

(10) quaternary diammonium polymer containing repeating unitscorresponding to formula (XV):

in which formula (XV):

R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different, representaliphatic, alicyclic or arylaliphatic radicals containing from 1 to 6carbon atoms or lower hydroxyalkylaliphatic radicals, or alternativelyR₁₀, R₁₁, R₁₂ and R₁₃, together or separately, constitute, with thenitrogen atoms to which they are attached, heterocycles optionallycontaining a second heteroatom other than nitrogen, or alternativelyR₁₀, R₁₁, R₁₂ and R₁₃ represent a linear or branched C₁-C₆ alkyl radicalsubstituted with a nitrile, ester, acyl or amide group or a group—CO—O—R₁₄-D or —CO—NH—R₁₄-D where R₁₄ is an alkylene and D is aquaternary ammonium group;

A1 and B1 represent polymethylene groups containing from 2 to 8 carbonatoms, which may be linear or branched and saturated or unsaturated andmay contain, bonded to or intercalated in the main chain, one or morearomatic rings, or one or more oxygen or sulfur atoms, or sulfoxide,sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium,ureido, amide or ester groups, and

X⁻ denotes an anion derived from a mineral or organic acid;

A1, R₁₀ and R₁₂ can form, with the two nitrogen atoms to which they areattached, a piperazine ring; in addition, if A1 denotes a linear orbranched, saturated or unsaturated alkylene or hydroxyalkylene radical,B1 can also denote a group —(CH₂)n-CO-D-OC—(CH₂)n- in which D denotes:

a) a glycol residue of formula: —O—Z—O—, where Z denotes a linear orbranched hydrocarbon-based radical or a group corresponding to one ofthe following formulae:—(CH₂—CH₂—O)x-CH₂—CH₂—[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)—

-   -   where x and y denote an integer from 1 to 4, representing a        defined and unique degree of polymerization or any number from 1        to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue, such as a piperazine derivative;

c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y denotesa linear or branched hydrocarbon-based radical, or else the divalentradicalCH₂—CH₂—S—S—CH₂—CH₂—;

d) a ureylene group of formula: —NH—CO—NH—.

Preferably, X⁻ is an anion, such as chloride or bromide.

These polymers have a number-average molecular weight generally between1000 and 100 000.

Polymers of this type are especially described in French patents 2 320330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and U.S. Pat. Nos.2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002,2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193,4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

It is more particularly possible to use polymers that are formed fromrepeating units corresponding to formula (XVI) below:

in which R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbonatoms approximately, n and p are integers ranging from 2 to 8approximately, and X⁻ is an anion derived from a mineral or organicacid. Mention may be made in particular of Mexomer PO sold by thecompany Chimex;

(11) Polyquaternary ammoniums formed from repeating units of formula(XVII):

in which p denotes an integer ranging from 1 to 6 approximately, D maybe nothing or may represent a group —(CH₂)_(r)—CO— in which r denotes anumber equal to 4 or 7, and X⁻ is an anion.

Such polymers may be prepared according to the processes described inU.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are especiallydescribed in patent application EP-A-122 324.

Among these polymers, examples that may be mentioned include theproducts Mirapol A 15, Mirapol AD1, Mirapol AZ1 and Mirapol 175 sold bythe company Miranol;

(12) quaternary polymers of vinylpyrrolidone and of vinylimidazole, forinstance the products sold under the names Luviquat FC 905, FC 550 andFC 370 by the company BASF. These polymers may also comprise othermonomers, for instance diallyldialkylammonium halides. Mention may bemade in particular of the product sold under the name Luviquat Sensationby the company BASF;

(13) polyamines such as Polyquart H sold by Henkel, which is given underthe reference name Polyethylene glycol (15) Tallow Polyamine in the CTFAdictionary, or oxyethylenated (15 OE) coconut polyamines.

Other cationic polymers that may be used in the context of the inventionare polyalkyleneimines, in particular polyethyleneimines, polymerscontaining vinylpyridine or vinylpyridinium units, condensates ofpolyamines and of epichlorohydrin, polyquaternary ureylenes and chitinderivatives.

Among all the cationic polymers that may be used in the context of thepresent invention, it is preferred to use polymers of families (1), (2),(3), (4), (9), (10) and (12).

Preferably, the cationic polymer(s) are chosen from cationic celluloses,cationic guar gums and dimethyldiallylammonium halide homopolymers orcopolymers.

More preferentially, the cationic polymer(s) are chosen fromhydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- orhydroxypropyl-celluloses grafted especially with amethacryloyl-ethyltrimethylammonium,methacrylamidopropyl-trimethylammonium or dimethyldiallylammonium salt,cationic guar gums, and dimethyldiallylammonium chloride homopolymers orcopolymers.

The content of cationic polymer(s) in the composition according to theinvention may range from 0.05% to 5% by weight relative to the totalweight of the composition, preferably from 0.1% to 3% by weight and morepreferentially from 0.2% to 1.5% by weight relative to the total weightof the composition.

Fatty Substances

Preferably, the composition according to the invention comprises one ormore fatty substances.

For the purposes of the present invention, the term “fatty substance” isintended to mean an organic compound that is insoluble in water atordinary ambient temperature (20-25° C.) and at atmospheric pressure(760 mmHg, i.e. 1.013×10⁵ Pa), with a solubility in water of less than5%, preferably less than 1% and even more preferentially less than 0.1%.The fatty substances generally have in their structure ahydrocarbon-based chain comprising at least 6 carbon atoms. In addition,the fatty substances are generally soluble in organic solvents under thesame temperature and pressure conditions, for instance chloroform,ethanol, benzene, liquid petroleum jelly ordecamethylcyclopentasiloxane.

The fatty substances are, moreover, non-(poly)oxyalkylenated andnon-(poly)glycerolated. In other words, the fatty substances do notcomprise in their structure a (poly)ethylene oxide or (poly)glycerol or(poly)propylene glycol unit.

Preferably, the fatty substance(s) are present in the compositionaccording to the invention in a total content ranging from 0.1% to 20%by weight, preferably from 1% to 15% by weight and more preferentiallyfrom 3% to 10% by weight relative to the total weight of thecomposition.

Preferably, the composition according to the invention comprises a totalcontent of fatty substances of greater than or equal to 3% by weightrelative to the total weight of the composition.

The fatty substance(s) may be chosen from solid fatty substances and/orliquid fatty substances (also called “oil”), and mixtures thereof.

The term “oil” is intended to mean a “fatty substance” that is liquid,i.e. that is capable of flowing under the action of its own weight atambient temperature (25° C.) and at atmospheric pressure (760 mmHg, i.e.1.013×10⁵ Pa). Preferably, the viscosity at a temperature of 25° C. andat a shear rate of 1 s⁻¹ of the oil is between 10⁻³ Pa·s and 2 Pa·s. Itmay be measured using a Thermo Haake RS600 rheometer with cone-plategeometry or an equivalent machine.

For the purposes of the present invention, the term “solid fattysubstance” is intended to mean a fatty substance that is not liquid atambient temperature (20-25° C.) and atmospheric pressure (760 mmHg, i.e.1.013×10⁵ Pa), in particular a solid compound or a compound having aviscosity of greater than 2 Pa·s at a shear rate of 1 s⁻¹ under theconditions mentioned above.

The solid fatty substances used in the composition according to theinvention have a melting point greater than ambient temperature,preferably a melting point greater than or equal to 40° C.,preferentially ranging from 46 to 95° C.

In particular, the fatty substance may be chosen from hydrocarbon-basedfatty substances, silicone-based fatty substances other than the aminosilicones previously described, and/or fluorinated fatty substances.

The term “hydrocarbon-based fatty substance” is intended to mean a fattysubstance formed essentially of, or even constituted of, carbon andhydrogen atoms, and optionally of oxygen or nitrogen atoms, and notcomprising any silicon or fluorine atoms. It may contain alcohol, ester,ether, carboxylic acid, amine and/or amide groups.

The hydrocarbon-based fatty substance may in particular be chosen fromhydrocarbons, fatty substances of animal origin, fatty substances ofplant origin, fatty alcohols, fatty esters and fatty ethers.

According to a first embodiment, the fatty substance may be asilicone-based fatty substance.

The term “silicone-based fatty substance” is intended to mean a fattysubstance containing at least one silicon atom. The term “non-siliconefatty substance” is intended to mean a fatty substance not containingany silicon (Si) atoms.

According to one embodiment, the silicone-based fatty substance otherthan amino silicones may be a liquid silicone oil (aka silicone oil orliquid silicone). The term “liquid silicone” is intended to mean anorganopolysiloxane that is liquid at ordinary temperature (25° C.) andat atmospheric pressure (760 mmHg; i.e. 1.013×10⁵ Pa).

Preferably, the silicone is chosen from liquid polydialkylsiloxanes, inparticular liquid polydimethylsiloxanes (PDMSs), and liquidpolyorganosiloxanes comprising at least one aryl group.

The polydialkylsiloxanes are in particular chosen frompolydimethylsiloxanes comprising trimethylsilyl end groups, andpolydimethylsiloxanes comprising dimethylsilanol end groups, known underthe name dimethiconol (CTFA). The polyorganosiloxanes comprising arylgroups are in particular chosen from polydiarylsiloxanes, in particularpolydiphenylsiloxanes, and polyalkylarylsiloxanes.

According to a second embodiment, the fatty substance may befluorinated. The term “fluorinated fatty substance” is intended to meana fatty substance containing at least one fluorine atom.

In particular, by way of fluorinated fatty substance, mention may bemade of fluorinated oils such as perfluoromethylcyclopentane andperfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 andFlutec® PC3 by the company BNFL Fluorochemicals;perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such asdodecafluoropentane and tetradecafluorohexane, sold under the names PF5050® and PF 5060® by the company 3M, or alternativelybromoperfluorooctyl sold under the name Foralkyl® by the companyAtochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane;perfluoromorpholine derivatives such as 4-trifluoromethylperfluoromorpholine sold under the name PF 5052® by the company 3M.

According to a preferred third embodiment, the fatty substance is ahydrocarbon-based fatty substance as defined above. In particular,preferably, the hydrocarbon-based fatty substance(s) are chosen fromhydrocarbon-based oils and hydrocarbon-based solid fatty substances, andmixtures thereof. Preferably, the hydrocarbon-based fatty substance(s)are advantageously chosen from hydrocarbons containing more than 16carbon atoms, C₆-C₁₆ alkanes, triglycerides or oils of plant origin,liquid synthetic triglycerides, fatty alcohols, esters of fatty acidsand/or of fatty alcohols other than triglycerides and non-siliconewaxes, or mixtures thereof.

According to a first variant of the invention, the hydrocarbon-basedfatty substance is an oil.

Preferably, the hydrocarbon-based oils are chosen from:

halogenated or non-halogenated linear or branched hydrocarbons, ofmineral or synthetic origin, containing less than 16 carbon atoms, forinstance hexane, cyclohexane, undecane, dodecane, isododecane ortridecane, or more than 16 carbon atoms, such as liquid petroleum jelly,liquid paraffin, polydecenes of formula C10nH[(20n)+2] in which n rangesfrom 3 to 9 and preferably from 3 to 7, and mixtures thereof;

unsaturated or branched liquid fatty alcohols comprising from 6 to 30carbon atoms, such as those of formula CnH2n+1OH with n an integerbetween 6 and 20 inclusive. Mention may be made especially of oleylalcohol, linolenyl alcohol, linoleyl alcohol, ricinoleyl alcohol,undecylenyl alcohol, isostearyl alcohol and octyldodecanol;

triglyceride oils of plant or synthetic origin, such as liquid fattyacid triglycerides comprising from 6 to 30 carbon atoms, for instanceheptanoic or octanoic acid triglycerides, or alternatively, for example,sunflower oil, maize oil, soy bean oil, marrow oil, grapeseed oil,sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil,castor oil, avocado oil, caprylic/capric acid triglycerides, forinstance those sold by the company Stéarineries Dubois or those soldunder the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel,jojoba oil and shea butter oil; and

liquid esters other than triglycerides.

These esters are preferably liquid esters of saturated or unsaturated,linear or branched, C₁-C₂₆ aliphatic monoacids or polyacids and ofsaturated or unsaturated, linear or branched, C₁-C₂₆ aliphaticmonoalcohols or polyalcohols, the total number of carbon atoms in theesters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among thealcohol and the acid from which the esters of the invention are derivedis branched.

Among the monoesters of monoacids and of monoalcohols, mention may bemade of ethyl palmitate, isopropyl palmitate, alkyl myristates such asisopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexylisononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C₁-C₂₂alcohols and esters of mono-, di- or tricarboxylic acids and of C₄-C₂₆non-sugar di-, tri-, tetra- or pentahydroxylated alcohols may also beused.

Mention may in particular be made of: diethyl sebacate; diisopropylsebacate; diisopropyl adipate; di(n-propyl) adipate; dioctyl adipate;diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate; tridecylerucate; triisopropyl citrate; triisostearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl,isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetylor 2-octyldodecyl myristate, hexyl stearate, propylene glycoldicaprylate, butyl stearate, isobutyl stearate; dioctyl malate, hexyllaurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.

The composition may further comprise, as liquid fatty ester, sugaresters and diesters of C₆-C₃₀ fatty acids, preferably C₁₂-C₂₂ fattyacids. It is recalled that the term “sugar” is intended to meanoxygen-bearing hydrocarbon-based compounds containing several alcoholfunctions, with or without aldehyde or ketone functions, and whichcomprise at least 4 carbon atoms. These sugars may be monosaccharides,oligosaccharides or polysaccharides.

The hydrocarbon-based oils are preferably chosen from the polydecenes offormula C10nH[(20n)+2] in which n ranges from 3 to 9 and preferably from3 to 7, fatty alcohols, esters and in particular esters of fattyalcohols or of fatty acids, sugar esters or diesters of C₁₂-C₂₄ fattyacids, cyclic esters, cyclic ethers, mineral oils, plant oils or animaloils, or mixtures thereof.

Preferably, the liquid fatty substance(s) are chosen from thepolydecenes of formula C10nH[(20n)+2] in which n ranges from 3 to 9 andpreferably from 3 to 7, fatty alcohols, such as octyldodecanol orisostearyl alcohol, esters of fatty alcohols or of fatty acids, liquidpetroleum jelly and liquid paraffin, and mixtures thereof.

When the composition according to the invention comprises one or moreliquid fatty substances, the fatty substance(s) that are liquid atambient temperature are preferably present in the composition accordingto the invention in a total content ranging from 0.1% to 20% by weight,preferably from 1% to 15% by weight and more preferentially from 3% to10% by weight relative to the total weight of the composition.

According to a second preferred variant of the invention, thecomposition according to the invention comprises at least one solidfatty substance, which is preferably hydrocarbon-based. The compositionaccording to the invention thus comprises one or more solid,hydrocarbon-based fatty substances.

Preferably, the solid fatty substance(s) are chosen from fatty alcohols,and esters of fatty acids and/or of fatty alcohols, and/or waxes, andalso mixtures thereof.

According to one preferred embodiment, the solid fatty substance(s) arehydrocarbon-based fatty substances, preferably chosen from solid fattyalcohols and/or solid esters of fatty acids and/or fatty alcohols.Preferably, the solid hydrocarbon-based fatty substances are chosen fromlinear or branched, saturated or unsaturated solid fatty alcoholscomprising from 14 to 30 carbon atoms and/or solid esters derived fromC₉-C₂₆ fatty acids and from C₉-C₂₆ fatty alcohols.

Preferably, the solid fatty alcohols are saturated or unsaturated, andlinear or branched, and comprise from 14 to 30 carbon atoms. Preferably,the fatty alcohol(s) are chosen from saturated and linear fatty alcoholscomprising from 14 to 30 and preferably from 16 to 22 carbon atoms.

In addition, it is understood that the fatty alcohols do not compriseC₂-C₃ oxyalkylenated unit(s) or glycerolated unit(s).

Preferably, the solid fatty substance(s) are chosen from cetyl alcohol,stearyl alcohol, behenyl alcohol and a mixture thereof. Cetylstearylalcohol may for example be used.

The hydrocarbon-based solid fatty substance(s) can also be chosen fromsolid esters of fatty acids and/or of fatty alcohols; mention may inparticular be made of the solid esters derived from C₉-C₂₆ fatty acidsand from C₉-C₂₆ fatty alcohols.

In particular, these esters may be chosen from octyldodecyl behenate,isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate,cetyl octanoate, decyl oleate, myristyl stearate, octyl palmitate, cetylpalmitate, octyl pelargonate, octyl stearate, alkyl myristates such ascetyl myristate, myristyl myristate or stearyl myristate, and hexylstearate.

Preferably, the fatty substance(s) that are solid at ambient temperatureare present in the composition according to the invention in a totalcontent ranging from 0.1% to 20% by weight, preferably from 1% to 15% byweight and more preferentially from 3% to 10% by weight relative to thetotal weight of the composition.

Preferably, the composition according to the invention comprises one ormore non-silicone, more particularly solid, fatty substances.

Additional Direct Dyes

The composition according to the invention may optionally comprise atleast one additional direct dye conventionally used for the dyeing ofkeratin fibres. It may be chosen from cationic and non-ionic species.

Non-limiting examples that may be mentioned include nitrobenzene dyes,azo, azomethine, methine, tetraazapentamethine, anthraquinone,naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthene,phenanthridine and phthalocyanin dyes, and natural dyes, alone or asmixtures.

It may be chosen, for example, from the following red or orangenitrobenzene dyes: 1-hydroxy-3-nitro-4-N-(γ-hydroxypropyl)aminobenzene,N-(β-hydroxyethyl)amino-3-nitro-4-aminobenzene,1-amino-3-methyl-4-N-(β-hydroxyethyl)amino-6-nitrobenzene,1-hydroxy-3-nitro-4-N-(β-hydroxyethyl)aminobenzene,1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-methylaminobenzene,N-(β-hydroxyethyl)-2-nitro-para-phenylenediamine,1-amino-2-nitro-4-(β-hydroxyethyl)amino-5-chlorobenzene,2-nitro-4-aminodiphenylamine, 1-amino-3-nitro-6-hydroxybenzene,1-(β-amino ethyl)amino-2-nitro-4-(β-hydroxyethyloxy)benzene,1-(β,γ-dihydroxypropyl)oxy-3-nitro-4-(β-hydroxyethyl)aminobenzene,1-hydroxy-3-nitro-4-aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene,1-methoxy-3-nitro-4-(β-hydroxyethyl)aminobenzene,2-nitro-4′-hydroxydiphenylamine and1-amino-2-nitro-4-hydroxy-5-methylbenzene.

The additional direct dye may also be chosen from yellow andgreen-yellow nitrobenzene direct dyes. Examples that may be mentionedinclude the compounds chosen from:1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene,1-methylamino-2-nitro-5-(β,γ-dihydroxypropyl)oxybenzene,1-(β-hydroxyethyl)amino-2-methoxy-4-nitrobenzene, 1-(β-aminoethyl)amino-2-nitro-5-methoxybenzene,1,3-di(β-hydroxyethyl)amino-4-nitro-6-chlorobenzene,1-amino-2-nitro-6-methylbenzene,1-(β-hydroxyethyl)amino-2-hydroxy-4-nitrobenzene,N-(β-hydroxyethyl)-2-nitro-4-trifluoromethylaniline,4-(β-hydroxyethyl)amino-3-nitrobenzenesulfonic acid,4-ethylamino-3-nitrobenzoic acid,4-(β-hydroxyethyl)amino-3-nitrochlorobenzene,4-(β-hydroxyethyl)amino-3-nitromethylbenzene,4-(β,γ-dihydroxypropyl)amino-3-nitrotrifluoromethylbenzene,1-(β-ureidoethyl)amino-4-nitrobenzene, 1,3-diamino-4-nitrobenzene,1-hydroxy-2-amino-5-nitrobenzene,1-amino-2-[tris(hydroxymethyl)methyl]amino-5-nitrobenzene,1-(β-hydroxyethyl)amino-2-nitrobenzene and4-(β-hydroxyethyl)amino-3-nitrobenzamide.

Mention may also be made of blue or violet nitrobenzene direct dyes, forinstance1-(β-hydroxyethyl)amino-4-N,N-bis(β-hydroxyethyl)amino-2-nitrobenzene,1-(γ-hydroxypropyl)amino-4-N,N-bis(β-hydroxyethyl)amino-2-nitrobenzene,1-(β-hydroxyethyl)amino-4-(N-methyl-N-β-hydroxyethyl)amino-2-nitrobenzene,1-(β-hydroxyethyl)amino-4-(N-ethyl-N-β-hydroxyethyl)amino-2-nitrobenzene,1-(β,γ-dihydroxypropyl)amino-4-(N-ethyl-N-β-hydroxyethyl)amino-2-nitrobenzene,and the 2-nitro-para-phenylenediamines of formula (III) below:

in which:

-   -   R_(B) represents a C₁-C₄ alkyl radical or a β-hydroxyethyl,        β-hydroxypropyl or γ-hydroxypropyl radical;    -   R_(A) and R_(C), which may be identical or different, represent        a β-hydroxyethyl, β-hydroxypropyl, γ-hydroxypropyl or        β,γ-dihydroxypropyl radical, at least one of the radicals R_(B),        R_(C) or R_(A) representing a γ-hydroxypropyl radical and R_(B)        and R_(C) not being able simultaneously to denote a        β-hydroxyethyl radical when R_(B) is a γ-hydroxypropyl radical,        such as those described in French patent FR 2 692 572.

Among the azo direct dyes that may be used according to the invention,mention may be made of the cationic azo dyes described in patentapplications WO 95/15144, WO 95/01772, EP 714954, FR 2 822 696, FR 2 825702, FR 2 825 625, FR 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369 and FR 2 844269.

Among these compounds, mention may be made most particularly of thefollowing dyes:1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium halides,1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium halides,1-methyl-4-[(methylphenylhydrazono)methyl]-pyridinium halides or alkylsulfates.

Among the azo direct dyes, mention may also be made of the followingdyes, described in the Colour Index International 3rd edition: DisperseRed 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, BasicYellow 57, Basic Brown 16, Acid Yellow 36, Acid Orange 7, Acid Red 33,Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, DisperseBlack 9.

Mention may also be made of1-(4′-aminodiphenylazo)-2-methyl-4-bis(β-hydroxyethyl)aminobenzene and4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic acid.

Among the quinone direct dyes, mention may be made of the followingdyes:

Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1,Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3,Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22, DisperseViolet 15, Basic Blue 99, and also the following compounds:1-N-methylmorpho liniumpropylamino-4-hydroxyanthraquinone,1-aminopropylamino-4-methylamino anthraquinone, 1-aminopropylaminoanthraquinone, 5-β-hydroxyethyl-1,4-diamino anthraquinone,2-aminoethylaminoanthraquinone,1,4-bis(β,γ-dihydroxypropylamino)anthraquinone.

Among the azine dyes, mention may be made of the following compounds:Basic Blue 17, Basic Red 2.

Among the indoamine dyes that may be used according to the invention,mention may be made of the following compounds:2β-hydroxyethylamino-5-[bis(β-4′-hydroxyethyl)amino]anilino-1,4-benzoquinone,2β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone,3-N-(2′-chloro-4′-hydroxy)phenylacetylamino-6-methoxy-1,4-benzoquinoneimine,3-N(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimineand3-[4′-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine.

Among the dyes of tetraazapentamethine type that may be used accordingto the invention, mention may be made of the following compounds:2-((E)-{(E)-[(1,3-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene)hydrazono]methyl}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumchloride;2-{(E)-[(1Z)-N-(1,3-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene)ethanehydrazonoyl]diazenyl}-1,3-dimethyl-1H-imidazol-3-ium chloride;4-methoxy-2-((E)-{(1E)-1-[(2E)-(4-methoxy-1-methylpyridin-2(1H)-ylidene)hydrazono]ethyl}diazenyl)-1-methylpyridinium chloride;1-methyl-2-((E)-{(1E)-1-[(2E)-(1-methylpyridin-2(1H)-ylidene)hydrazono]ethyl}diazenyl)pyridinium chloride;1-(2-hydroxyethyl)-2-[(E)-((1E)-1-{(2E)-[1-(2-hydroxyethyl)pyridin-2(1H)-ylidene]hydrazono}ethyl)diazenyl]pyridinium chloride;1-methyl-2-((E)-{(E)-[(2Z)-(1-methylpyridin-2(1H)-ylidene)hydrazono]methyl}diazenyl)pyridiniumchloride;1-(2-hydroxyethyl)-2-[(E)-((E)-{(2E)-[1-(2-hydroxyethyl)pyridin-2(1H)-ylidene]hydrazono}methyl)diazenyl]pyridinium acetate.

Among the additional natural direct dyes that may be used according tothe invention, mention may be made of lawsone, juglone, alizarin,purpurin, carminic acid, kermesic acid, purpurogallin,protocatechaldehyde, indigo, isatin, curcumin, spinulosin andapigenidin. Use may also be made of extracts or decoctions comprisingthese natural dyes and in particular henna-based poultices or extracts.

When they are present, the content of additional direct dyes in thecomposition generally ranges from 0.001% to 20% and preferably from0.01% to 10% by weight relative to the weight of the composition.

Other Additives

The composition according to the invention may also contain variousadjuvants conventionally used in hair dyeing compositions, such asanionic, non-ionic, amphoteric or zwitterionic polymers or mixturesthereof; mineral thickeners, and in particular fillers such as clays ortalc; antioxidants; penetrants; sequestrants; fragrances; dispersants;film-forming agents; ceramides; preservatives; opacifiers.

The above adjuvants are generally present in an amount for each of themof between 0.01% and 20% by weight relative to the weight of thecomposition or by weight of the ready-to-use composition.

Needless to say, those skilled in the art will take care to select thisor these optional additional compound(s) such that the advantageousproperties intrinsically associated with the dyeing composition that isuseful in the context of the invention are not, or are notsubstantially, adversely affected by the envisaged addition(s).

The dyeing composition that is useful in the context of the inventionmay be in various forms, such as in the form of liquids, creams or gels,or in any other form that is suitable for dyeing keratin fibres, andespecially human hair.

Process

The process for dyeing keratin fibres, in particular human keratinfibres such as the hair, consists in applying to said fibres thecomposition according to the invention.

In particular, the dyeing composition used in the process according tothe invention is applied to wet or dry keratin fibres.

It is usually left in place on the fibres for a time generally of from 1minute to 1 hour and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process conventionally ranges fromambient temperature (between 15° C. and 25° C.) to 80° C., preferablyfrom ambient temperature to 60° C.

After the treatment, the human keratin fibres are advantageously rinsedwith water. They may optionally be washed with a shampoo, followed byrinsing with water, before being dried or left to dry.

Use

The present invention also relates to the use of the dyeing compositionas defined previously for dyeing keratin fibres, in particular humankeratin fibres such as the hair.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

EXAMPLES

In the examples that follow, the colour build-up (ΔE_(ab)*) wasevaluated in the CIE L*a*b* system.

In this L*a*b* system, L* represents the intensity of the colour, a*indicates the green/red colour axis and b* the blue/yellow colour axis.The lower the value of L*, the darker or more intense the colour.

The value of ΔE_(ab)* was calculated from the values of L*a*b* accordingto equation (i) below:ΔE _(ab)*=√{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b_(o)*)²)}  (i)

The colour build-up (ΔE_(Lab)*) was calculated from the colorimetricvalues for locks of untreated hair (L₀*, a₀* and b₀*) and locks of dyedhair (L*, a* and b*).

The greater the value of ΔE_(ab)*, the better the colour build-up forthe treated fibres.

In the examples that follow, all the amounts are given as weightpercentages of active materials relative to the total weight of thecomposition, unless otherwise indicated.

I. Example 1

a. Compositions Tested

Compositions (A1), (B1), (A2) and (B2) below were prepared from theingredients as described below, the contents of which are indicated ingram % (unless otherwise mentioned) in Table 1 below.

Compositions A1 and B1 are compositions according to the invention, thepH of which is acidic (pH 3.5), and comprising respectively the cationicdirect dyes of triarylmethane structure Basic Blue 77 (also known as HCBlue 15) and Basic Violet 2.

Compositions A2 and B2 are comparative compositions outside theinvention, the pH of which is basic (pH 9).

TABLE 1 A1 A2 B1 B2 Inven- Compar- Inven- Compar- tion ative tion ativeSodium hydroxide pH = 3.5 pH = 9 pH = 3.5 pH = 9 Citric acid 0.025 0.0250.025 0.025 Basic Blue 77 0.2 0.2 — — (HC Blue No. 15) Basic Violet 2 —— 0.1 0.1 Cetylstearyl Alcohol 3.75 3.75 3.75 3.75 (50/50 C16/C18) CetylAlcohol 1 1 1 1 Hydroxyethylcellulose 0.2 0.2 0.2 0.2 (MW: 1 300 000Hydroxypropyl guar 0.1 0.1 0.1 0.1 trimethylammonium chloridePolydimethylsiloxane 2 2 2 2 containing aminoethyl aminopropyl groups,containing methoxy and/ or hydroxyl and alpha- omega silanol functions,as a cationic 60% aqueous emulsion (1) Deionized water qs 100 qs 100 qs100 qs 100 Preservatives qs qs qs qs Behenyltrimethyl- 2.6 2.6 2.6 2.6ammonium chloride as an aqueous solution containing 79% am

(1) Amodimethicone (and) Trideceth-6 (and) cetrimonium chloride soldunder the reference Xiameter MEM-8299 Emulsion by Dow Corning

b. Direct Dyes Tested

The direct dyes used in compositions (A1), (B1), (A2) and (B2) areindicated in Table 2 below.

TABLE 2

BASIC BLUE 77 (HC BLUE No 15)

BASIC VIOLET 2

c. Procedure

Compositions A1, A2, B1 and B2 are applied to locks of hair that is verysensitized owing to bleaching, in a proportion of 5 g of composition per1 g of hair.

After a leave-on time of 20 minutes at ambient temperature, the locksare rinsed with clear water, then dried.

d. Evaluation

The colorimetric measurements are performed using a Minolta CM2006Dspectrocolorimeter (illuminant D65, angle 10°, specular componentincluded) in the CIELab system.

e Results

The results are reported in Table 3 below.

TABLE 3 L* B1 - BV2 pH 3.5 31.42 B2 - BV2 pH 9 36.22 A1 - BV77 pH 3.526.93 A2 - BV77 pH 9 34.56

The power is represented by the value of L*: the lower the value of L*,the more powerful the colour obtained.

As shown by the table above, the compositions according to the invention(A1 and B1) formulated at acidic pH allowing much greater colour powerobtained at acidic pH.

II. Example 2

a Compositions Tested

Compositions (C1), (C2) and (D) below were prepared from the ingredientsas described below, the contents of which are indicated in gram %(unless otherwise mentioned) in Table 4 below.

Compositions C1 and C2 are compositions according to the invention, thepH of which is acidic, and comprising respectively the cationic directdyes of triarylmethane structure Basic Blue 77 (also known as HC Blue15) and Basic Blue 1. Composition D is a comparative composition outsidethe invention, the pH of which is acidic, but which comprises as directdye Basic Blue 99 which is not a direct dye of triarylmethane structure.

TABLE 4 C1 C2 D (invention) (invention) (comparative) Sodium HydroxidepH = 3.5 pH = 3.5 pH = 3.5 Basic Blue 77 (HC Blue 0.5 — — No. 15) BasicBlue 1 — 0.5 — Basic Blue 99 — — 0.5 Cetyl alcohol 0.95 0.95 0.95 Guar0.1 0.1 0.1 Hydroxypropyltrimonium Chloride Cetearyl Alcohol 3.75 3.753.75 Preservative qs qs qs Amodimethicone 1.15 1.15 1.15 BehentrimoniumChloride 2 2 2 Citric acid 0.025 0.025 0.025 Hydroxyethylcellulose 0.20.2 0.2 Water qs 100 qs 100 qs 100

e. Direct Dyes Tested

The direct dyes used in compositions (C1), (C2) and (D) are indicated inthe table below:

Basic Blue 77 (HC Blue No 15)

Basic Blue No 1

Basic Blue 99

f. Procedure

Compositions C1, C2 and D are applied to locks of natural haircontaining 90% grey hairs, in a proportion of 5 g per gram of hair.

After a leave-on time of 20 minutes at ambient temperature, the locksare rinsed with clear water, then dried.

g. Evaluation

The colorimetric measurements are performed using a Minolta CM2006Dspectrocolorimeter (illuminant D65, angle 10°, specular componentincluded) in the CIELab system.

h. Results

The results are reported in Table 5 below.

TABLE 5 L* a* b* ΔE Non-dyed hair 63.66 2.07 16.43 C1 25.31 5.55 −32.5562.30 (invention) C2 23.49 −16.61 −13.78 53.62 (invention) D 21.24 1.24−7.46 48.96 (comparative)

Compositions C1 and C2 according to the invention result in a betterbuildup of the colour compared with comparative composition D.

The invention claimed is:
 1. A process for dyeing human hair,comprising: applying to human hair a composition comprising, in acosmetically acceptable medium of acidic pH less than 5, at least onecationic direct dye of triarylmethane structure.
 2. The processaccording to claim 1, wherein the pH of the composition ranges from 1 to4.9.
 3. The process according to claim 1, wherein the cationic directdye of triarylmethane structure is chosen from the cationic dyes offormula (I)

or the organic or mineral, acid or base addition salts thereof, thegeometrical isomers, optical isomers, or tautomers thereof, themesomeric forms thereof, or the solvates or hydrates thereof; wherein informula (I): A, B and C are identical or different, and each representsa (hetero)aryl group which is optionally substituted, and ═ represents asingle bond or a double bond.
 4. The process according to claim 1,wherein the cationic direct dye of triarylmethane structure is chosenfrom the cationic dyes of formulae (IIa) and (II′a) below:

or the organic or mineral, acid or base addition salts thereof, thegeometrical isomers, optical isomers, or tautomers thereof, themesomeric forms thereof, or the solvates or hydrates thereof: wherein informulae (IIa) and (II′a) below: R1, R2, R3 and R4, which may beidentical or different, each represents a hydrogen atom or a(C1-C6)alkyl group which is optionally substituted with a hydroxylgroup, an aryl group, phenyl, an aryl(C1-C4)alkyl group, benzyl, aheteroaryl, or a heteroaryl(C1-C4)alkyl group, or else two groups R1 andR2, and/or R3 and R4, borne by the same nitrogen atom, form, togetherwith the nitrogen atom which bears them, an optionally substitutedheterocycloalkyl group, morpholino, piperazino, or piperidino; R5, R6,R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16, which may beidentical or different, each represents a hydrogen atom, a halogen atom,or a group chosen from i) hydroxyl; ii) thiol; iii) amino; iv)(di)(C1-C4)(alkyl)amino; v) (di)arylamino or (di)phenylamino; vi) nitro;vii) acylamino (—NR—C(O)R′) in which the radical R is a hydrogen atom ora C1-C4 alkyl radical optionally bearing at least one hydroxyl group,and the radical R′ is a C1-C2 alkyl radical; viii) carbamoyl((R)₂N—C(O)—) in which the radicals R, which may be identical ordifferent, represent a hydrogen atom or a C1-C4 alkyl radical optionallybearing at least one hydroxyl group; ix) carboxylic acid or ester,(—O—C(O)R′) or (—C(O)OR′), in which the radical R′ is a hydrogen atom,or C1-C4 alkyl optionally bearing at least one hydroxyl group and theradical R′ is a C1-C2 alkyl radical; x) alkyl optionally substituted inparticular with a hydroxyl group; xi) alkylsulfonylamino (R′SO₂—NR—) inwhich the radical R represents a hydrogen atom or a C1-C4 alkyl radicaloptionally bearing at least one hydroxyl group and the radical R′represents a C1-C4 alkyl radical or a phenyl radical; xii) aminosulfonyl((R)₂N—SO2-) in which the radicals R, which may be identical ordifferent, represent a hydrogen atom or a C1-C4 alkyl radical optionallybearing at least one hydroxyl group; xiii) (C1-C4)alkoxy; or xiv)(C1-C4)alkylthio; or else two radicals borne by two contiguous carbonatoms R5 and R6 and/or R7 and R8 and/or R9 and R10 and/or R11 and R12and/or R13 and R14 and/or R15 and R16 form, together with the carbonatoms which bear them, an aryl or heteroaryl, said ring being optionallysubstituted; Q- represents an anionic counterion for achievingelectroneutrality.
 5. The process according to claim 1, wherein thecationic direct dye of triarylmethane structure is chosen from those offormula (IIa) or (II′a), wherein, taken together or separately: R1, R2,R3 and R4 each represents a hydrogen atom, a (C1-C4)alkyl group, methyl,or ethyl, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 eachrepresents a hydrogen atom, a halogen atom, chlorine, a (C1-C4)alkylgroup, methyl, ethyl, an amino group, or a (di)(C1-C4)(alkyl)aminogroup.
 6. The process according to claim 1, wherein the cationic directdye of triarylmethane structure is chosen from Basic Violet 1, BasicViolet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1,Basic Blue 7, Basic Blue 26, Basic Green 1, Basic Blue 77, or mixturesthereof.
 7. The process according to claim 1, wherein the total amountof cationic direct dye of triarylmethane structure ranges from 0.0001%to 10% by weight, relative to the total weight of the composition. 8.The process according to claim 1, wherein the composition furthercomprises at least one amino silicone, chosen from the silicones offormula (B) below:R′aG3-a-Si(OSiG2)n-(OSiGbR′2-b)m-O—SiG3-a-R′a  (B) wherein: G, which maybe identical or different, denotes a hydrogen atom or a phenyl, OH,C₁-C₈ alkyl, methyl, C₁-C₈ alkoxy, or methoxy group, a, which may beidentical or different, represents 0 or an integer from 1 to 3, bdenotes 0 or 1, m and n are numbers such that the sum (n+m) ranges from1 to 2000, wherein n represents a number from 0 to 1999 and m representsa number from 1 to 2000; R′, which may be identical or different,represents a monovalent radical of formula —CqH2qL in which q is anumber ranging from 2 to 8 and L is an optionally quaternized aminogroup chosen from —N(R″)2; —N+(R″)3 A-; —NR″-Q-N(R″)2, or —NR″-Q-N+(R″)3A-, wherein: R″, which may be identical or different, representshydrogen, phenyl, benzyl, a saturated monovalent hydrocarbon-basedradical, a C1-C20 alkyl radical; Q denotes a linear or branched CrH2rgroup, r being an integer ranging from 2 to 6; and A- represents acosmetically acceptable anion, a halide, fluoride, chloride, bromide, oriodide.
 9. The process according to claim 8, wherein the amino siliconeis chosen from the silicones of formula (F) below:

wherein: m and n are numbers such that the sum (n+m) ranges from 1 to2000, wherein n represents a number from 0 to 1999, and m represents anumber from 1 to 2000; A denotes a linear or branched alkylene radicalcontaining from 4 to 8 carbon atoms.
 10. The process according to claim8, wherein the total amount of the amino silicone ranges from 0.01% to10% by weight, relative to the total weight of the composition.
 11. Theprocess according to claim 1, wherein the composition comprises at leastone surfactant.
 12. The process according to claim 11, wherein the atleast one surfactant is chosen from cetyltrimethylammonium,behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammoniumsalts, and mixtures thereof.
 13. The process according to claim 1,further comprising at least one fatty substance in a total amount ofgreater than or equal to 3% by weight, relative to the total weight ofthe composition.
 14. The process according to claim 1, furthercomprising at least one additive chosen from a thickening polymer, acationic polymer, an additional direct dye other than the dyes oftriarylmethane structure, or mixtures thereof.
 15. The process accordingto claim 12, wherein the surfactant is chosen frombehenyltrimethylammonium chloride, cetyltrimethylammonium chloride, anddipalmitoylethyl-hydroxyethylmethylammonium methosulfate, and mixturesthereof.